ORCID Profile
0000-0002-6966-6121
Current Organisation
Monash University
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Research Topics
In Research Link Australia (RLA), "Research Topics" refer to ANZSRC FOR and SEO codes. These topics are either sourced from ANZSRC FOR and SEO codes listed in researchers' related grants or generated by a large language model (LLM) based on their publications.
Top 5 Research Topics
ANZSRC Field of Research (FoR)
Inorganic Chemistry | F-Block Chemistry | Bioinorganic Chemistry | Main Group Metal Chemistry | Main Group Metal Chemistry | F-Block Chemistry | Organometallic Chemistry | Transition Metal Chemistry | Solid State Chemistry | Physical Chemistry (Incl. Structural) | Organometallic Chemistry | Chemical Spectroscopy | F-block chemistry | Main group metal chemistry | Structural Chemistry | Organometallic chemistry | Physical Chemistry of Materials | Solid State Chemistry | Optical Properties of Materials | Biological And Medical Chemistry | Synthesis of Materials | Organic Chemical Synthesis | Transition Metal Chemistry | Organic Chemical Synthesis | Bioinorganic Chemistry | Nanochemistry and Supramolecular Chemistry | Inorganic Green Chemistry | Electrochemistry | Physical Organic Chemistry | Inorganic chemistry | Industrial Chemistry | Inorganic Chemistry Not Elsewhere Classified | Toxicology (Incl. Clinical Toxicology) | Analytical Biochemistry | Organic Chemistry Not Elsewhere Classified | Clinical Chemistry | Risk Engineering (excl. Earthquake Engineering) |
ANZSRC Socio-Economic Objective (SEO)
Chemical sciences | Expanding Knowledge in the Chemical Sciences | Treatments (e.g. chemicals, antibiotics) | Diagnostics | Organic industrial chemicals not classified elsewhere | Higher education | Other | Diagnostic methods | Expanding Knowledge in Engineering | Reconstituted products (e.g. chipboard, particle board)
Related Links
Publications
The Synthesis of Organometallics by Decarboxylation Reactions
Publisher: Elsevier
Date: 1986
Reactions of lanthanoid metals with 3,5-diphenylpyrazole at elevated temperatures: synthesis and structures of both homoleptic, [Ln3(Ph2pz)9] (Ln = La, Nd), [Ln2<
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B400541D
Abstract: The direct reaction of lanthanoid metals with 3,5-diphenylpyrazole (Ph2pzH) at 300 degrees C under vacuum in the presence of mercury gives the structurally characterized [Ln3(Ph2pz)9] (Ln = La or Nd), [Ln2(Ph2pz)6] (Ln = Er or Lu). Similar reactions provided heteroleptic [Ln(Ph2pz)3(Ph2pzH)2] (Ln = La, Nd, Gd, Tb, Er and Y). The last was obtained only from impure Ph2pzH, but was subsequently prepared by treatment of [Yb(Ph2pz)3(thf)2] with Ph2pzH. Reactions of Yb with Ph2pzH at 200 degrees C gave a poorly soluble alent species which was converted by 1,2-dimethoxyethane into [Yb(Ph2pz)2(dme)2]. Single crystal X-ray structures established a bowed trinuclear pyrazolate-bridged structure for [Ln3(Ph2pz)9] (Ln = La or Nd), Ln...Ln...Ln being 135.94(1) degrees (La) and 137.41(1) degrees(Nd). There are two eta2-Ph2pz ligands on the terminal Ln atoms and one on the central metal with adjacent Ln atoms linked by one mu-eta2:eta2 and one mu-eta5 (to terminal Ln):eta2 pyrazolate group. Thus the terminal Ln atoms are formally nine-coordinate and the central Ln, ten-coordinate. By contrast, [Ln2(Ph2pz)6] (Ln = Er or Lu) complexes are dimeric with two terminal (eta2) and two bridging (mu-eta2:eta2) pyrazolates and eight-coordinate lanthanoids. All six heteroleptic complexes [Ln(Ph2pz)3(Ph2pzH)2] (Ln = La, Nd, Gd, Tb, Er or Yb) are isomorphous with three equatorial eta2-Ph2pz groups, transoid(N-Ln-N 158.18(6)-161.43(9) degrees) eta1-pyrazole ligands, and eight-coordinate Ln throughout.
Organomercury compounds
Publisher: Elsevier BV
Date: 07-1988
η6:η6 Coordination of Tetraphenylborate to Ytterbium(II ): A New Class of Lanthanoid ansa‐Metallocenes
Publisher: Wiley
Date: 03-2005
The preparation and crystal structure of bis(cyclopentadienyl)(2,6-diphenylphenoxo)bis(tetrahydrofuran)neodymium(III); an unexpected example of formal nine coordination
Publisher: Elsevier BV
Date: 05-1991
Far infrared and Raman spectra of some crystalline halomercurate(II) complexes
Publisher: CSIRO Publishing
Date: 1966
DOI: 10.1071/CH9661603
Abstract: The infrared spectra (500-40 cm-1) of crystalline (Me4N)2HgCl4, Me4NHgCl3, and (Et4As)2HgI4, and the Raman spectra of the first two compounds, have been recorded. Assignments of the vibrational frequencies are made and discussed in relation to the structure of the anions.
Tetramethylammonium hexanitratolanthanate(III) methanol solvate
Publisher: International Union of Crystallography (IUCr)
Date: 26-07-2006
Organolanthanoids. XII. Reactions of bis(cyclopentadienyl)ytterbium(II) with some diorganomercurials
Publisher: Elsevier BV
Date: 02-1988
MakingCarexmonophyletic (Cyperaceae, tribe Cariceae): a new broader circumscription
Publisher: Oxford University Press (OUP)
Date: 14-07-2015
DOI: 10.1111/BOJ.12298
LnIII2MnIII2 heterobimetallic “butterfly” complexes displaying antiferromagnetic coupling (Ln = Eu, Gd, Tb, Er)
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT31144E
Abstract: The isostructural heterometallic complexes [Ln(III)(2)Mn(III)(2)O(2)(ccnm)(6)(dcnm)(2)(H(2)O)(2)] (Ln = Eu (1Eu), Gd (1Gd), Tb (1Tb), Er (1Er) ccnm = carbamoylcyanonitrosomethanide dcnm = dicyanonitrosomethanide) have been synthesised and structurally characterised. The in situ transition metal promoted nucleophilic addition of water to dcnm, forming the derivative ligand ccnm, plays an essential role in cluster formation. The central [Ln(III)(2)Mn(III)(2)(O)(2)] moiety has a "butterfly" topology. The coordinated aqua ligands and the NH(2) group of the ccnm ligands facilitate the formation of a range of hydrogen bonds with the lattice solvent and neighbouring clusters. Magnetic measurements generally reveal weak intracluster antiferromagnetic coupling, except for the large J(MnMn) value in 1Gd. There is some evidence for single molecule magnetic (SMM) behaviour in 1Er. Comparisons of the magnetic properties are made with other recently reported butterfly-type {Ln(III)(x)M(III)(4-x) (d-block)} clusters, x = 1, 2 M = Mn, Fe.
Synthesis and structures of di(2-pyridyl)amine diruthenium(I) complexes, including an example of monodentate coordination
Publisher: Elsevier BV
Date: 11-2003
HRTEM studies of defects and interdiffusion in Hg1−x−yMnyCdxTe (O⩽x, y⩽1) grown by low temperature MOCVD
Publisher: Elsevier BV
Date: 1991
Organomercury compounds. XXII. Syntheses of polybromophenylmercurials by decarboxylation reactions
Publisher: CSIRO Publishing
Date: 1977
DOI: 10.1071/CH9771013
Abstract: The mercuric polybromobenzoates, (C6Br2CO2)2Hg, (XC6Br4CO2)2Hg (X = p-F, p-Cl, p-Me, o-Me, p-MeO or m-MeO) and (2,6-Me2C6Br3CO2)2Hg, and phenylmercuric pentabromobenzoate have been prepared by reaction of mercuric acetate or phenylmercuric acetate with the appropriate polybromobenzoic acids. Thermal decomposition of (C6Br5CO2)2Hg, (XC6Br4CO2)2Hg, (X = p-F, p-Cl or p-MeO) and C6Br5C02HgPh in boiling pyridine gave the new polybromophenylmercurials (C6Br& Hg, (XC6Br4)2Hg and C6Br5HgPh respectively, but similar treatment of (XC6Br4C02)2Hg (X = p-Me, o-Me or m-MeO) and (2,6-Me2C6Br3C02)2Hg yielded pyridine complexes of the mercuric carboxylates. Mercuric p-methyltetrabromobenzoate underwent decarboxylation in boiling nitrobenzenelpyridine giving (p-MeC6Br4),Hg, but the method could not be extended to (0-Mec~Br~C0~)o~r H(2g,6 -Me2C6Br,C02)2Hg. Decarboxylation of XC6Br4C02H (X = o-Me or m-MeO) was effected in molten mercuric trifluoroacetate giving, after treatment of the products with sodium chloride, the corresponding tetrabromophenylmercuric chlorides. All mercurials underwent cleavage with iodine or triiodide ions in hot dimethylformamide to give the corresponding iodopolybromobenzenes, and (C6Br5)2Hg was converted into C6Br5HgX (X = C1 or Br) by the corresponding mercuric halides in hot xylene/nitrobenzene. Thermal symmetrization of C6Br5HgX (X = C1, Br, or Ph) is detectable prior to melting, but (C6Br5),Hg is stable to at least 400'. The mass spectra of the polybromophenylmercurials are discussed.
The X-ray crystal structures of [Hg(C6F4OH-p)2OH2] and [Hg(C6H4OMe-p)(O2CC6F4OMe-p)] – Factors influencing supramolecular Hg–O interactions
Publisher: Elsevier BV
Date: 11-2005
The Supramolecular Architecture of Arene Complexes of Bis(polyfluorophenyl)mercurials
Publisher: Wiley
Date: 10-2008
Abstract: The 1:1 (arene)mercury complexes [HgR 2 (arene)] [R = C 6 F 4 ‐ o ‐NO 2 , C 6 F 4 ‐ m ‐NO 2 , C 6 F 4 ‐ o ‐H, C 6 F 5 arene = TMB (1,2,4,5‐tetramethylbenzene), PMB (1,2,3,4,5‐pentamethylbenzene)] are readily formed when mixtures of the mercurial and arene are crystallised from CH 2 Cl 2 or CH 2 Cl 2 /hexane. Analogous 1:1 complexes are also formed from Hg(C 6 F 5 ) 2 and PhMe, whereas novel 1:2 complexes [HgR 2 (arene) 2 ] result from Hg(C 6 F 4 ‐ o ‐NO 2 ) 2 and PhMe or TMO (1,2,4‐trimethoxybenzene) and from Hg(C 6 F 5 ) 2 and TMO. In the crystalline state, the 1:1 [HgR 2 (arene)] complexes exist as canted columns of alternating planar HgR 2 and arene layers linked by weak (Hg ··· C 3.2–3.5 Å) η 1 or η 2 π‐arene–mercury interactions. For the TMB (R = C 6 F 4 ‐ o ‐NO 2 , C 6 F 4 ‐ o ‐H, C 6 F 5 ) and PhMe (R = C 6 F 5 ) complexes, the packing of neighbouring columns shows aligned, alternating fluoroarene and arene ring planes resulting in a 2D brick‐wall motif with potential supramolecular components (fluoroarene–fluoroarene and fluoroarene–arene stacking). For the TMB complex with R = C 6 F 4 ‐ m ‐NO 2 the 2D array is distorted into a herringbone motif by weak C–H ··· O interactions. The 1:2 complex [Hg(C 6 F 4 ‐ o ‐NO 2 ) 2 (PhMe) 2 ] has an analogous mercury environment to the 1:1 complexes, and the packing shows a distinct layer structure of alternating rows of PhMe and HgR 2 with two PhMe units per HgR 2 unit but with no inter‐stack interactions. The TMO complexes have long Hg ··· O contacts (3.2 Å) rather than Hg ··· C and similarly show a layered structure, but in this case, with a single column of alternating HgR 2 and pairs of TMO. Theoretical calculations for the 1:2 [HgR 2 (TMB) 2 ] complexes (R = C 6 F 4 ‐ o ‐NO 2 , C 6 F 4 ‐ m ‐NO 2 ) are consistent with the findings from the observed crystal structures. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Atypical pharmacokinetics and excretion of new platinum analogues in rodents
Publisher: Springer Science and Business Media LLC
Date: 2002
DOI: 10.1007/S00280-001-0381-7
Abstract: Two new series of platinum complexes with cytotoxic activity in vivo are [Pt(NRCH2)2L2], (R=polyfluorophenyl, L=pyridine or substituted pyridine) and [Pt(NRCH2CH2NR'2)2L(X)], (R, L as before R'=Me or Et, X=halogen). The aim of this study was to determine the pharmacokinetics and excretion in mice and in isolated perfused rat livers of a representative compound from each class, respectively: Pt103 (R=p-HC6F4, L=pyridine) and Pt109 (R, L as for Pt103, R'=Et, X=I). Mice were given intraperitoneal injections of active doses of Pt103, Pt109, or cisplatin in a variety of vehicles. Blood was s led at several times to 48 h. Some mice were placed in metabolic cages where urine and feces were collected. In isolated, perfused rat livers, perfusate and bile were collected following a dose of Pt103, cisplatin or carboplatin. Platinum was measured in blood, urine, feces, or perfusate by atomic absorption spectroscopy. Three vehicles used were peanut oil, dimethyl sulphoxide, and saline/Tween 20. In contrast to renal excretion of over 70% for cisplatin in saline, urinary excretion of platinum was less than 24% of a dose of Pt109 in peanut oil, less than 21% of P103 in DMSO, and only 4% for Pt103 in peanut oil. Over 60% of Pt103 was eliminated in mouse feces, and 57% was excreted in bile from rat liver. Plasma protein binding of Pt109 was greater than 90% at 6 h following administration in mice. In contrast to cisplatin and carboplatin, representatives of two new classes of platinum anticancer agents undergo minimal renal elimination, but are excreted mainly in the bile and feces. If a platinum complex with a similar excretion profile was introduced into the clinic, there might be a therapeutic advantage in terms of drug toxicity and combination therapy with other cytotoxics.
Characterization of low-temperature MOCVD Cd1−xMnxTe thin films
Publisher: Elsevier BV
Date: 1991
Organolanthanoids. XXI Synthesis of Bis- and Tris-(diphenylphosphinocyclopenta- dienyl)lanthanoid Compounds and the X-Ray Crystal Structures of [Ln(C5H4PPh2)3(OPPh3)]·(thf)1
Publisher: CSIRO Publishing
Date: 1997
DOI: 10.1071/C97125
Abstract: Redox transmetallation ofTl(C5H4PPh2)with an excess of Sm in refluxing thf (thf = tetrahydrofuran) or Eu indme (dme = 1,2-dimethoxyethane) at room temperature gave thelanthanoid(II) compounds[Sm(C5H4PPh2)2](1) and[Eu(C5H4PPh2)2(dme)](2). Crystallization of (1) or[Yb(C5H4PPh2)2(dme)]with OPPh3 in dme yielded[Sm(C5H4PPh2)2(OPPh3)2](3) and[Yb(C5H4PPh2)2(OPPh3)2](4). Room-temperature transmetallation ofTl(C5H4PPh2)with Nd gave the lanthanoid(III) compound[Nd(C5H4PPh2)3(thf)](5), but analogous reactions with La, Pr, Er, Gd and Y in refluxing thfgenerally gave intractable oils, although in one instance impure[La(C5H4PPh2)3(thf)]·(thf)0 · 5,namely(6)·(thf)0 · 5, wasisolated. This complex was also obtained at room temperature by usingLaI3-activated La metal. Oxidation of (1) with 1 equiv.ofTl(C5H4PPh2)in toluene yielded solvent-freeSm(C5H4PPh2)3(7). Addition of OPPh3 to these systems allowed theisolation of[Ln(C5H4PPh2)3(OPPh3)]·(thf)x(x = 0-1 · 5 Ln = La (8), Pr (9),Nd (10), Sm (11), Er (12), Y (13)). Single-crystal X-ray structuredetermination of(10)·(thf)1 · 5,(11)·(thf)1 · 5 and(12)·(thf)1 · 5revealed formally 10-coordinate complexes with an O-bondedOPPh3, threeη5-C5H4PPh2ligands and lattice thf. The centroids of the C5 ringsand the oxygen atom surround the central metal in a distorted tetrahedralarray.
Organolanthanoids
Publisher: Elsevier BV
Date: 09-1985
New decarbonylation reactions of carbonylruthenium(II) complexes
Publisher: Elsevier BV
Date: 1982
EPR spectroscopic characterization of a monomeric Pt III species produced via electrochemical oxidation of the anticancer compound trans -[Pt II {( p -HC 6 F 4 )NCH 2 CH 2 NEt 2 }Cl(py)]
Publisher: Elsevier BV
Date: 09-2016
DOI: 10.1016/J.JINORGBIO.2016.01.015
Abstract: The bulk oxidative electrolysis of a 2mM solution of trans-[Pt
Structural and reactivity consequences of reducing steric bulk of N,N-diarylformamidinates coordinated to lanthanoid ions
Publisher: Wiley
Date: 04-09-2014
Organotin Compounds as Reagents for the Synthesis of Lanthanoid Complexes by Redox Transmetallation Reactions
Publisher: Wiley
Date: 22-08-2006
Correlated substituent rotation in the 1,2-benzenedisulfonate anion: the structure of the hydrated potassium salt
Publisher: Informa UK Limited
Date: 25-08-2009
Synthesis and structural diversity of rare earth anthranilate complexes
Publisher: Elsevier BV
Date: 2006
Structural Isomers of Bis(diphenylarsino)methane‐dichloroplatinum(II)
Publisher: Wiley
Date: 16-02-2004
Organomercury compounds. X. Reactions of diarylmercurials with arenesulphinic and -sulphonic acids
Publisher: CSIRO Publishing
Date: 1970
DOI: 10.1071/CH9701275
A divalent heteroleptic lanthanoid fluoride complex stabilised by the tetraphenylcyclopentadienyl ligand, arising from C–F activation of pentafluorobenzene
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4CC04427D
Abstract: The alent heteroleptic lanthanoid fluoride complex, [Yb(C 5 Ph 4 H)(μ-F)(thf) 2 ] 2 , as well as [Yb(C 5 Ph 4 H) 2 (thf)] and [Yb(C 5 Ph 4 H)(C 6 F 5 )(thf) 2 ] were obtained from reactions of ytterbium metal with Hg(C 6 F 5 ) 2 and tetraphenyl–cyclopentadiene under different conditions.
Preparation and cell growth inhibitory activity of [PtR2L2] (R=polyfluorophenyl, L2=diene, cyclohexane-1,2-diamine (chxn) or cis-(dimethyl sulfoxide)2) and the X-ray crystal structure of [Pt(C6F5)2(ci
Publisher: Elsevier BV
Date: 04-2002
DOI: 10.1016/S0162-0134(02)00363-X
Abstract: A range of [PtR(2)(chxn)] (R=C(6)F(5), o-HC(6)F(4), p-HC(6)F(4), p-MeOC(6)F(4) or 3,5-H(2)C(6)F(3) chxn=cyclohexane-1,2-diamine) and cis-[PtR(2)(dmso)(2)] (R=C(6)F(5), p-HC(6)F(4) or p-MeOC(6)F(4) dmso=dimethyl sulfoxide) complexes have been prepared from the corresponding [PtR(2)(diene)] (diene=cis,cis-cycloocta-1,5-diene (cod), hexa-1,5-diene (hex), norbornadiene (nbd) or dicyclopentadiene (dcy)) derivatives and have been spectroscopically characterized. A representative crystal structure of [Pt(C(6)F(5))(2)(cis-chxn)] was determined and shows a slightly distorted square planar geometry for platinum with chxn virtually perpendicular to the coordination plane. The biological activity against L1210 and L1210/DDP cell lines of these compounds together with the behaviour of other organoplatinum complexes, [PtR(2)L(2)] (L(2)=ethane-1,2-diamine (en) or cis-(NH(3))(2)) have been determined. Despite the use of relatively inert fluorocarbon anions as leaving groups, moderate-high cell growth inhibitory activity is observed. None of the fluorocarbon complexes displayed any cross resistance with cisplatin.
Crystal Structure of Di[(μ-benzoato-O,O′)bis(η5-methylcylopentadienyl)ytterbium(III)]
Publisher: Wiley
Date: 07-2001
DOI: 10.1002/1521-3749(200107)627:7<1431::AID-ZAAC1431>3.0.CO;2-T
Rare earth 3-(4′-hydroxyphenyl)propionate complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5NJ00787A
Abstract: Structural variation of lanthanoid 3-(4′-hydroxyphenyl)propionates and investigation of the anti-corrosion properties of lanthanum 3-(4′-hydroxyphenyl)propionate are presented, highlighting lanthanoid contraction and the importance of the –CHCH− structural unit of 4-hydroxycinnamates in corrosion mitigation.
Organomercury compounds. VIII. The preparation of pentafluorophenylmercury compounds by mercuration reactions
Publisher: CSIRO Publishing
Date: 1968
DOI: 10.1071/CH9682675
Abstract: Pentafluorophenylmercuric carboxylates, C6F5HgOCOR (R = CF3, CHF2, CH2F, or CH3), have been prepared by reaction of pentafluorobenzene with the appropriate mercuric carboxylate. The compounds are monomeric in toluene, and their infrared spectra suggest the presence of unidentate carboxylate groups. Mercuration of pentafluorobenzene with mercuric trifluoroacetate, followed by reaction of the crude product with sodium iodide in aqueous ethanol, gives a good yield of bispentafluorophenylmercury.
The Structure of di-μ-chlorobis[bis(2,3,5,6-tetraflourophenyl)-(triphenylphosphine oxide)thalliium(III)]
Publisher: Elsevier BV
Date: 07-1980
Metal-sulphur stretching frequencies and structures of complexes of zinc, cadmium, and mercury with thiols
Publisher: Elsevier BV
Date: 1976
Decarboxylation syntheses of transition metal organometallics
Publisher: Elsevier BV
Date: 08-1992
The influence of organic structure and rare earth metal cation on the corrosion efficiency observed on AS1020 steel compared with La(4OHCin)3
Publisher: American Institute of Mathematical Sciences (AIMS)
Date: 2015
Organoamido- and Aryloxo-Lanthanoids. V. Preparations of Low-Coordinate Lanthanoid(II) Phenolates, Ln (OC6H2But2-2,6-X-4)2( thf )n (Ln = Yb or Eu; X = H, Me or BuT; N = 2 or 3) and the X-Ray Crystal S
Publisher: CSIRO Publishing
Date: 1993
DOI: 10.1071/CH9930387
Abstract: Lanthanoid (II) complexes of bulky aryl oxides, Ln (OC6H2But2-2,6-X-4)2 ( Ln = Yb or Eu X = H, Me or But) have been prepared by one or more of the following methods: ( i ) reaction of Ln (C6F5)2 with the appropriate phenol, (ii) reaction of the lanthanoid metal, Hg(C6F5)2 and the phenol, and (iii) reaction of the lanthanoid metal with the corresponding thallium(I) phenolate, in tetrahydrofuran ( thf ), and they have been isolated as Ln (OC6H2But2-2,6-X-4)2(thf)3 complexes. Crystallization of Yb (OC6H2But2-2,6-X-4)2( thf )3 (X = H or Me) from toluene yields Yb (OC6H2But2-2,6-X-4)2( thf )2. The X-ray crystal structure of [ Yb (OC6H2But3-2,4,6)2( thf )3]. thf [monoclinic, a 10.20(1), b 32.97(2), c 16.018(4) Ǻ, β 93.52(8)°, V 5375 Ǻ3, Z 4, 2734 'observed' data refined to R 0.070] shows distorted square pyramidal five coordination for ytterbium with an apical thf oxygen [ Yb -O 2.44(1)Ǻ], and transoid phenolate oxygens [ Yb -O 2.21(1), 2.22(1)Ǻ, O- Yb -O 149.0(6)°] and trans thf oxygens [ Yb -O 2.47(2), 2.48(1)Ǻ, O-Yb -O 177.3(5)°] in the square plane. Four methyl groups ( Yb…C 3.89-4.15 Ǻ) across the square plane away from the apical oxygen may block coordination of an additional ligand. X-Ray structures of Yb (OC6H2But2-2,6-Me-4)2(thf)n showing four coordination (n = 2) and five coordination (n = 3), given in a preliminary communication,1 are further discussed.
Remarkable in vitro bactericidal activity of bismuth(III) sulfonates against Helicobacter pylori
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT31360J
Abstract: Four new tris-substituted bismuth(III) sulfonates of general formula [Bi(O(3)SR)(3)] (R = phenyl 1, p-tolyl 2, 2,4,6-mesityl 3 and S-(+)-10-c horyl 4) have been synthesised and characterised. Their synthesis by solvent-free (SF) and solvent-mediated (SM) methods has been explored and their activity against Helicobacter pylori has been investigated. The compounds 1-4 display a remarkable in vitro activity against three laboratory strains of H. pylori (B128, 26,695 and 251) with minimum inhibitory concentration (MIC) values as low as 0.049 μg mL(-1) for the strains B128 and 26,695, and 0.781 μg mL(-1) for the clinical isolate 251. This places most MIC values in the nano-molar region and demonstrates the strong influence of the sulfonate group on the bactericidal properties. The novel solid state structure [Bi(8)(O(3)SMes)(20)(SO(4))(2)(H(2)O)(6)]·(C(7)H(8))(7)5·(C(7)H(8))(7), derived from the SM reaction under reflux conditions, is presented and the incorporation of the two inorganic sulfate anions in the centre of the wheel-like bismuth sulfonate cluster explained.
The synthesis and structure of heteroleptic tris(diimine)ruthenium(II) complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B401761G
Abstract: The reactions of bidentate diimine ligands (L2) with cationic bis(diimine)[Ru(L)(L1)(CO)Cl]+ complexes (L, L1, L2 are dissimilar diimine ligands), in the presence of trimethylamine-N-oxide (Me3NO) as a decarbonylation reagent, lead to the formation of heteroleptic tris(diimine) ruthenium(II) complexes, [Ru(L)(L1)(L2)]2+. Typically isolated as hexafluorophosphate or perchlorate salts, these complexes were characterised by UV-visible, infrared and mass spectroscopy, cyclic voltammetry, microanalyses and NMR spectroscopy. Single crystal X-ray studies have elucidated the structures of K[Ru(bpy)(phen)(4,4'-Me(2)bpy)](PF(6))(3).1/2H(2)O, [Ru(bpy)(5,6-Me(2)phen)(Hdpa)](ClO(4))(2), [Ru(bpy)(phen)(5,6-Me(2)phen)](ClO(4))(2), [Ru(bpy)(5,6'-Me(2)phen)(4,4'-Me(2)bpy)](PF(6))(2).EtOH, [Ru(4,4'-Me(2)bpy)(phen)(Hdpa)](PF(6))(2).MeOH and [Ru(bpy)(4,4'-Me(2)bpy)(Hdpa)](ClO(4))(2).1/2Hdpa (where Hdpa is di(2-pyridyl)amine). A novel feature of the first complex is the presence of a dinuclear anionic adduct, [K(2)(PF(6))(6)](4-), in which the two potassium centres are bridged by two fluorides from different hexafluorophosphate ions forming a K(2)F(2) bridging unit and by two KFPFK bridging moieties.
Rare-earth metalation of calix[4]pyrrole/calix[4]arene free of alkali-metal companions
Publisher: American Chemical Society (ACS)
Date: 08-05-2012
DOI: 10.1021/OM2011134
Electrochemistry, Protein Binding and Crystal Structures of Platinum(II) and Platinum(IV) Carboxylato Complexes
Publisher: CSIRO Publishing
Date: 2002
DOI: 10.1071/CH02086
Abstract: The crystal structures of the platinum(II) complexes [Pt(ox)(en)] (ox = oxalato, en = ethane-1,2-diamine) and [Pt(ethmal)(en)] (ethmal = ethylmalonato), and of their platinum(IV) analogues, trans-[Pt(OH)2(ox)(en)].H2O and trans-[Pt(ethmal)(OH)2(en)], have been determined. All crystallize in the monoclinic space group P21/c, with the exception of trans-[PtIV(OH)2(ox)(en)].H2O which crystallizes in C2/c. The ethylmalonato ligand in [PtII(ethmal)(en)] adopts a pseudo-boat conformation. Changes in the fold angles of the boat occur on oxidation and introduction of the trans hydroxo ligands. The cathodic forward half-wave potentials of the platinum(iv) complexes (including trans-[Pt(mal)(OH)2(en)], mal = malonato) are reported and reveal that these complexes are more difficult to reduce than analogous complexes with equatorial chloro ligands. The binding of trans-[Pt(OH)2(ox)(en)].H2O and trans-[Pt(mal)(OH)2(en)] to mouse albumin was investigated with no binding observed after 6 h and a very small amount observed for the latter complex after 24 h.
Organothallium compounds
Publisher: Elsevier BV
Date: 10-1980
Transmetallation reactions involving phenylenemercurials
Publisher: Elsevier BV
Date: 1987
Crystal structure of ethane-1,2-diaminebis(2,3,5,6-tetrafluoro-4-methoxyphenyl) platinum(II), C16H14F8N2O2Pt
Publisher: Walter de Gruyter GmbH
Date: 12-2002
The thallation of polyfluoroaromatic compounds
Publisher: Elsevier BV
Date: 08-1977
A convenient synthesis of lanthanoid trihalides in tetrahydrofuran
Publisher: Elsevier BV
Date: 1979
A Structural Investigation of Trivalent and Divalent Rare Earth Thiocyanate Complexes Synthesised by Redox Transmetallation
Publisher: Wiley
Date: 06-2010
Abstract: A wide range of reactive trivalent and alent rare earth thiocyanate complexes with 1,2‐dimethoxyethane (dme), tetrahydrofuran (thf) and acetonitrile namely [RE(NCS) 3 (dme) 3 ] [RE = La ( 1a ), Nd ( 1b )], [RE(NCS) 3 (dme) 2 (μ‐dme) 0.5 ] 2 [RE = Dy ( 1d ), Er ( 1e )], [RE(NCS) 3 (thf) 4 ] 2 [RE = Y ( 3a ), La ( 3b ), Nd ( 3c ), Sm ( 3d ), Dy ( 3e ), Ho ( 3f )], [Ca(NCS) 2 (dme) 3 ] [ rac ‐( 4a )], [RE(NCS) 2 (dme) 3 ] (RE = Sm ( rac ‐ 4b ), Eu ( rac ‐ 4c ), [Ca(Yb)(NCS) 2 (NCMe) 5 ] · NCMe [Ca ( 6a ), Yb ( 6b )], and [Eu(NCS) 2 (thf) 4 ] 2 ( 7 ) have been prepared in good to high yield by redox transmetallation between rare earth metals and the commercially available Hg(SCN) 2 . In addition [Eu(NCS) 3 (dme) 2 (μ‐dme) 0.5 ] 2 ( 1c ) and [Yb(NCS) 3 (dme) 2 ] ( 1f ) have been prepared by oxidation of rac ‐ 4c and [Yb(NCS) 2 (thf) 2 ], respectively, with Hg(SCN) 2 in dme. Crystallisation of 1e from dme/diglyme (diglyme = bis(2‐methoxyethyl) ether) and thf yields [Er(NCS) 3 (diglyme)(dme)] ( 2 ) and [Er(NCS) 3 (thf) 4 ] 2 ( 3g ), respectively, and prolonged storage of rac ‐ 4a in cold dme gave [Ca(NCS) 2 (dme) 2 (H 2 O)] ( 5 ). All undergo rapid hydrolysis on exposure to air. Two structural breaks are observed for [RE(NCS) 3 (dme) n ] complexes, all of which have solely RE–NCS binding. Compounds 1a , b are nine‐coordinate monomers that differ in the arrangement (T or Y) of the RE(NCS) 3 moiety, 1c – e are eight coordinate dinuclear complexes being bridged by a single η 1 :η 1 ‐( O , O ′)‐dme and 1f is a seven coordinate monomer. 2 is an eight coordinate monomer with, unusually for the present complexes, a facial RE(NCS) 3 array. By contrast 3a – g are all dimeric, eight coordinate complexes with two unusual RE–NCS–RE bridges. The RE–S bonds are very weak and show little variation with RE 3+ radius, and Er–S of 3g increases by 0.18 Å between 123 K and room temperature), foreshadowing a change to a seven coordinate monomer with [Yb(NCS) 3 (thf) 4 ]. Monomeric eight coordination with transoid (N–RE–N ≈ 149°) SCN–RE–NCS bonding is observed in rac ‐ 4a – c and Λ‐ 4c , whilst 5 is a seven‐coordinate monomer with a cis ‐Ca(NCS) 2 array. Single crystals of 6 , a , b contain seven‐coordinate, pentagonal bipyramidal monomers with trans ‐NCS ligands, whereas 7 is dimeric with two Eu–NCS–Eu bridging ligands and seven coordination for Eu.
Bismuth(iii) 5-sulfosalicylate complexes: structure, solubility and activity against Helicobacter pylori
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B900774A
Abstract: Treatment of 5-sulfosalicylic acid (H(3)Ssal) with BiPh(3) results in the formation of the first dianionic carboxylate-sulfonate bismuth complex, [PhBi(HSsal)H(2)O](infinity) 1a, and its ethanol analogue [PhBi(HSsal)EtOH](infinity) 1b (space group P2(1)/c), while Bi(OAc)(3) gives the mixed monoanionic and dianionic complex, {[Bi(HSsal)(H(2)Ssal)(H(2)O)(3)](2) x 2 H(2)O}(infinity) 2 (space group P1). The three complexes are all polymeric in the solid state as determined by single crystal X-ray diffraction, with extended frameworks constructed from dimeric [Bi(HSsal)](2), 1a and 1b, or from [Bi(HSsal)(H(2)Ssal)](2) units, 2. The heteroleptic bismuth complexes 1a and 2 display remarkable aqueous solubility, 10 and 2.5 mg ml(-1) respectively, resulting in a clear solution of pH 1.5. In contrast, 1b is essentially insoluble in aqueous environments. All three complexes show significant activity against the bacterium Helicobacter pylori of <6.25 microg ml(-1).
Trispentafluorophenylbismuth
Publisher: Elsevier BV
Date: 03-1972
Novel rare earth quinolinolate complexes
Publisher: Elsevier BV
Date: 02-2008
Towards a Structural Understanding of the Anti‐Ulcer and Anti‐Gastritis Drug Bismuth Subsalicylate
Publisher: Wiley
Date: 21-08-2006
Selective monodecarbonylation of Ru(CO)2X2L2 complexes
Publisher: Elsevier BV
Date: 1981
Rare earth thiocyanate complexes with 18-crown-6 co-ligands
Publisher: Elsevier BV
Date: 03-2013
A Modern Twist to a Classic Synthetic Route: Ph
Publisher: American Chemical Society (ACS)
Date: 21-09-2017
DOI: 10.1021/ACS.INORGCHEM.7B00764
Abstract: This paper reports advances in redox transmetalation rotolysis (RTP) utilizing the readily available Ph
Preparations and ligand displacement reactions of diene(polyfluorophenyl)platinum(II) complexes
Publisher: Elsevier BV
Date: 03-1987
Reactions of uranium hydride with some organic and organometallic compounds
Publisher: Elsevier BV
Date: 1986
Palladium Complexes with the SC6F4H‐4 Ligand – Synthesis, Spectroscopy, and Structures
Publisher: Wiley
Date: 07-2013
Alkali‐Metal Pyrazolate Complexes with Unusual Pyrazolate Coordination Modes and Pseudocubane Motifs
Publisher: Wiley
Date: 26-03-2007
Abstract: The dimeric complex [Li(Ph2pz)(OEt2)]2 (1) and tetrameric cluster [Na(Ph2pz)(thf)]4 (2) were prepared by treatment of alkali-metal reagents (nBuLi and Na{N(SiMe3)2}, respectively) with 3,5-diphenylpyrazole (Ph2pzH) in Et2O (1) or THF (2). The polymer [Na(tBu2pz)]n (3) was obtained from reaction at elevated temperature in a sealed tube between Na metal and 3,5-di-tert-butylpyrazole (tBu2pzH). The complex [Na4(tBu2pz)2(thf)3(obds)]2 (4 obds = (OSiMe2)2O) was obtained as a minor product from prolonged treatment of tBu2pzH with elemental sodium in a silicone-greased flask. All four alkali-metal pyrazolato complexes were characterized by IR and 1H NMR spectroscopy and X-ray crystallography.The Li dimer 1 displays mu-eta(2):eta(1) lithium-pyrazolato binding, in which both lithium atoms are four-coordinate. Room- and variable-temperature NMR studies (1H, 13C, and 7Li) of 1 suggest similar behavior in solution, with peaks coalescing at low temperatures. Complexes 2 and 4 display distorted cubane structures. In 2, all the sodium atoms are five-coordinate, whereas 4 contains two sodium yrazolate/thf clusters (4:2:3 ratio) bridged by two obds(2-) units, as well as two four-coordinate and two five-coordinate sodium atoms. Compound 3 is composed of two independent chains with the unusual coordination modes mu3-eta(5):eta(2):eta(2), mu3-eta(5):eta(2):eta(1), and mu3-eta(4):eta(2):eta(1), with five-, six-, and seven-coordinate sodium atoms. Two oxo-centered M8 cage complexes [(tBu2pz)6Li8O] (5) and [(tBu2pz)6Na8O] (6) were obtained as by-products from attempted preparation of [Li(tBu2pz)] and [Na(tBu2pz)], respectively, and their structures were determined.
Permercurated arenes
Publisher: Elsevier BV
Date: 1974
Organoamidometallics. I syntheses of [N, N′-Bis(polyfiuorophenyl)ethane-1, 2-diaminato(2-)]platinum(II) complexes by decarboxylation
Publisher: CSIRO Publishing
Date: 1985
DOI: 10.1071/CH9862013
Abstract: Reaction of PtCl2(en) (en = ethane-1,2-diamine) with thallous pentafluorobenzoate in hot pyridine ( py ) or 4-methylpyridine ( mepy ) yields the [N,N′- bis (2,3,5,6-tetrafluorophenyl)ethane-1,2-diaminato(2-)]platinum(II) complexes, Pt[N(p-HC6F4)CH2]2( py )2 (1a) and Pt[N(p- HC6F4)CH2]2( mepy )2 (1b). The route to (1a) is considered to involve formation of [Pt(en)( py )2](O2CC6F5)2 (2), decarboxylation of (2) into Pt(NHCH2)2( py )2 (1c) and pentafluorobenzene, and nucleophilic attack of (1c) on C6F5H. Complex (1a) has also been prepared by decarboxylation of (2), reaction of PtI2(en) and TlO2CC6F5, and reaction of PtCl2(en), C6F5H, and TlO2CC6F4H-p in boiling pyridine. From reaction of PtCl2(en), TlO2CC6F4H-p, and the appropriate polyfluorobenzene (RF) in boiling pyridine or 4-methylpyridine, the organoamidoplatinum compounds Pt(NRCH2)2L2(R = C6F5, p-MeC6F4, p-ClC6F4, p-BrC6F4, p-IC6F4, 2,3,5-F3C6H2, or p-C6F5C6F4, L = py and R = C6F5, L = mepy ) have been prepared. Analogous reactions of PtCl2( pn )( pn = propane-1,3-diamine) give the complexes Pt[NR(CH2)3NR]( py )2 (R = C6F5 or p-HC6F4). Spectroscopic evidence for the structures is discussed. The polyfluorophenyl groups confer stability to water on ethane-1,2-diaminato(2-)platinum(II) complexes, and this is attributable to delocalization of non-bonded lone pairs from the amido nitrogens into the polyfluorophenyl rings.
Replacing Mercury: Syntheses of Lanthanoid Pyrazolates from Free Lanthanoid Metals, Pentafluorophenylsilver, and Pyrazoles, Aided by a Facile Synthesis of Polyfluoroarylsilver Compounds
Publisher: Wiley
Date: 06-02-2019
An Unexpected Coupling Reaction of 8-Quinolinolate at Elevated Temperature
Publisher: CSIRO Publishing
Date: 2014
DOI: 10.1071/CH14191
Abstract: Reactions of 8-hydroxyquinoline (HOQ) with elemental rare-earth and transition metal combinations or alloys at 200–300°C yielded a variety of complexes, albeit in very low yields, including two structurally characterised homometallic complexes containing an unexpected biquinolinolate ligand. Reaction of HOQ with SmCo5 alloy gives rise to the complexes [SmCo2(OQ)7] (1), [Co4(OQ)4(BQ)2] (2), and [Sm3(OQ)5(BQ)2(H2O)] (3Sm), where BQ is 2,7′-biquinoline-8,8′-diolate, resulting from an unusual coupling reaction between two OQ/HOQ species at the 2 and 7′ positions. Complexes 1–3 and HOQ co-crystal 2·2HOQ were isolated as single crystals from separate reactions although formation of other products under the reaction conditions used was likely. Analogues of 3Sm with erbium and ytterbium were obtained using respective rare-earth metal filing in combination with nickel powder. Reaction involving cobalt powder only, without any rare-earth metals, yielded a homoleptic complex containing only the 8-quinolinolate ligand i.e. [Co4(OQ)8] (4). These results highlight the rewards, in terms of rich synthetic chemistry, and pitfalls, in terms of yield and isolation, of the pseudo-solid state synthetic approach using 8-quinolinolate ligands.
Synthesis of perbromobenzoic acids and perbromobenzenes from aromatic carboxylic acids by permercuration and bromodemercuration
Publisher: CSIRO Publishing
Date: 1977
DOI: 10.1071/CH9770293
Abstract: Permercuration of the benzoic acids XC6H4CO2H (X = o-Me, F, Cl, or Br m- Me, F, Cl, Br, CF3, NO2 or OMe or p-Me, F, Cl, Br, CF3 or NO2) and 2,6- X2C6H3CO2H (X = Me, Cl, or Br) with molten mercuric trifluoroacetate at c. 180-245° followed by bromodemercuration gave the corresponding perbromobenzoic acids XC6Br4CO2H or 2,6-X2C6Br3CO2H, together with the corresponding perbromobenzenes C6Br5X or m-X2C6Br4 which were formed owing to decarboxylation under permercuration conditions. Similar treatment of the acids XC6H4CO2H (X = o-NO2, CF3, or OMe or p-OMe) and 2,6-F2C6H3CO2H gave only the appropriate perbromobenzenes. Possible mechanisms for permercuration induced decarboxylation are proposed on the basis of the effect of substituents on yields of perbromobenzoic acids and perbromobenzenes. Decarboxylation occurs more widely under permercuration conditions than on pyrolysis of mercuric carboxylates. Regiospecific mercuration meta to the carboxyl group and not decarboxylation occurred on thermal decomposition of mercuric p-methoxybenzoate.
A new twist on an old molecule: a rotameric isomer of bis(pentafluorophenyl)mercury
Publisher: Informa UK Limited
Date: 18-10-2021
Difunctionalization of primary aromatic amines with ethylene; synthesis of μ-arylnitrilobis(ethane-2,1-diyl)dimercury(II) complexes. Crystal structure of 2,4,6-Me3C6H2N-(CH2CH2HgCl)2
Publisher: Elsevier BV
Date: 10-1989
The chemistry of rare earth metals, compounds, and corrosion inhibitors
Publisher: Elsevier
Date: 2014
Lanthaballs: Chiral, Structurally Layered Polycarbonate Tridecanuclear Lanthanoid Clusters
Publisher: Wiley
Date: 08-05-2009
Abstract: New balls please! The viability of using carbonate as the primary anion in cluster formation is demonstrated in the synthesis of 'lanthaballs', spherical tridecanuclear lanthanoid complexes with a novel [Ln(CO(3))(6)] moiety in a [Ln(13)(CO(3))(14)] core (see picture). The chirality of the lanthaballs is evidenced in the configuration of extended columns of pi-stacked phenanthroline ligands. The structural and magnetic properties of lanthaballs are investigated.
Functionalised Alkaline Earth Iodides from Grignard Synthons “PhAeI(thf)n” (Ae = Mg‐Ba)
Publisher: Wiley
Date: 18-01-2019
Electrochemical and chemical oxidation of the antitumour agent Pt{((p-HC6F4)NCH2)(2)}(py)(2) - detection of platinum(III) intermediates
Publisher: Royal Society of Chemistry (RSC)
Date: 04-02-2003
DOI: 10.1039/B210815A
Organolanthanoids: XXII. The synthesis and X-ray structure of dimeric [YbCp2F(THF)]2 (Cp=cyclopentadienyl; THF=tetrahydrofuran)
Publisher: Elsevier BV
Date: 02-1998
Organoamido‐ and Aryloxo‐Lanthanoids, 17 Novel Low‐Coordinate Lanthanoid (II) and ‐(III) Aryloxide Complexes ‐ the X‐ray Structures of Bis (2,6‐diphenylphenolato) tris(tetrahydrofuran)‐ytterbium (II),
Publisher: Wiley
Date: 07-1997
Unprecedentedμ-η2:η2-Pyrazolate Coordination in [{Yb(η2-tBu2pz)(μ-η2:η2-tBu2pz)(thf)}2]
Publisher: Wiley
Date: 04-09-1998
DOI: 10.1002/(SICI)1521-3773(19980904)37:16<2251::AID-ANIE2251>3.0.CO;2-4
The use of ruthenium trifluoromethanesulphonates in the synthesis of [Ru(CO)2(bidentate)2]2+ complexes
Publisher: Springer Science and Business Media LLC
Date: 12-1980
DOI: 10.1007/BF01396948
Structural variations in rare earth benzoate complexes : Part I. Lanthanum
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B700980A
Decarboxylation syntheses of transition metal organometallics, II.trans-carbonyl(polyhalogenophenyl)bis(triphenylphosphine)rhodium(I) compounds
Publisher: Springer Science and Business Media LLC
Date: 12-1980
DOI: 10.1007/BF01396945
The reversal of sulphur dioxide insertion into metal-carbon bonds
Publisher: Elsevier BV
Date: 11-1968
A simple redox transmetallation synthesis of uranium tetrachloride and related preparations of uranium triiodide and chlorotris(cyclopentadienyl)uranium(IV)
Publisher: Elsevier BV
Date: 1988
Decarboxylation syntheses of transition metal organometallics. IV Polyfluorophenylpalladium(II) complexes
Publisher: Springer Science and Business Media LLC
Date: 06-1983
DOI: 10.1007/BF00956018
Preparatiions of chloro(diene)polyfluorophenylplatinum(II) complexes and the structure of chloro(dicyclopentadiene)-pentafluorophenylplatinum(II)
Publisher: Elsevier BV
Date: 1989
Rare Earth Complexes of Bulky 2,6-Diphenylphenolates Containing Additional, Potentially Buttressing 3,5-Substituents
Publisher: Wiley
Date: 06-2001
DOI: 10.1002/1099-0682(200106)2001:6<1505::AID-EJIC1505>3.0.CO;2-V
Synthesis and characterisation of alkaline earth bis(diphenylphosphano)metallocene complexes and heterobimetallic alkaline earth metal/platinum(ii ) complexes [Ae(thf)x(η5
Publisher:
Royal Society of Chemistry (RSC)
Date:
2012
DOI:
10.1039/C1DT11324K
Abstract: A series of alkaline earth metallocene complexes carrying the diphenylphosphanocyclopentadienyl ligand, [Ae(L)(x)(η(5)-C(5)H(4)PPh(2))(2)] (Ae = Ca, L = thf, x = 1 (6a) Ae = Ca, L = dme, x = 1 (6b) Ae = Sr, L = thf, x = 1 (7) Ae = Ba, L = thf, x = 1 (8a) Ae = Ba, L = dme, x = 2 (8b)), were prepared by redox transmetallation rotolysis from the free metals, diphenylmercury and diphenylphosphanocyclopentadiene. These complexes were characterised using multinuclear NMR spectroscopy and two by single crystal X-ray diffraction. [Ca(dme)(η(5)-C(5)H(4)PPh(2))(2)] (6b) is a discrete neutral monomeric eight coordinate molecule in which the phosphorus atoms are not coordinated to the calcium ion and the larger barium analogue, ten-coordinate [Ba(dme)(2)(η(5)-C(5)H(4)PPh(2))(2)] (8b), has an extremely bent sandwich structure due to the two dme ligands attached to the metal. Bimetallic complexes, [Ae(thf)(x)(η(5)-C(5)H(4)PPh(2))(2)Pt(Me)(2)].(solv) (Ae = Ca, L = thf, x = 2, solv = 1.5thf (9) Ae = Sr, L = thf, x = 3, solv = 1.5thf (10) Ae = Ba, L = thf, x = 3, solv = thf (11)) were obtained by reaction of the homometallic complexes with [Pt(cod)(Me)(2)]. The crystal structures of [Ca(thf)(2)(η(5)-C(5)H(4)PPh(2))(2)Pt(Me)(2)].1.5thf (9), [Sr(thf)(3)(η(5)-C(5)H(4)PPh(2))(2)Pt(Me)(2)].1.5thf (10) and [Ba(thf)(3)(η(5)-C(5)H(4)PPh(2))(2)Pt(Me)(2)].thf (11) show the eight (calcium) and nine coordinate (strontium and barium) fragments acting as a chelating metalloligand attached to the square planar platinum through the phosphorus donor atoms. The solution chemistry of these bimetallic complexes has been investigated by NMR spectroscopy, electro-spray ionisation mass spectrometry and conductivity experiments which indicate that the bimetallic compounds persist in solution.
Charge‐Separated and Molecular Heterobimetallic Rare Earth–Rare Earth and Alkaline Earth–Rare Earth Aryloxo Complexes Featuring Intramolecular Metal–π‐arene Interactions
Publisher: Wiley
Date: 19-05-2009
Abstract: Treatment of a rare earth metal (Ln) and a potential alent rare earth metal (Ln') or an alkaline earth metal (Ae) with 2,6-diphenylphenol (HOdpp) at elevated temperatures (200-250 degrees C) afforded heterobimetallic aryloxo complexes, which were structurally characterised. A charge-separated species [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] was obtained for a range of metals, demonstrating the similarities between the chemistry of the alent rare earth metals and the alkaline earth metals. The [(Ln'/Ae)(2)(Odpp)(3)](+) cation in the heterobimetallic structures is unusual in that it consists solely of bridging aryloxide ligands. A molecular heterobimetallic species [AeEu(Odpp)(4)] (Ae = Ca, Sr, Ba) was obtained by treating an alkaline earth metal and Eu metal with HOdpp at elevated temperatures. Similarly, [BaSr(Odpp)(4)] was prepared by treating Ba metal and Sr metal with HOdpp. Treatment of [Ba(2)(Odpp)(4)] with [Mg(Odpp)(2)(thf)(2)] in toluene afforded [Ba(2)(Odpp)(3)][Mg(Odpp)(3)(thf)]. Analogous solution-based syntheses were not possible for [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] complexes, for which the free-metal route was essential. As a result of the absence of additional donor ligands, the crystal structures of the heterobimetallic complexes feature extensive pi-Ph-metal interactions involving the pendant phenyl groups of the Odpp ligands, thus enabling the large electropositive metal atoms to attain coordination saturation. The charge-separated heterobimetallic species were purified by extraction with toluene/thf mixtures at ambient temperature (Ba-containing compounds) or by extraction with toluene under pressure above the boiling point of the solvent (other products). In donor solvents, heterobimetallic complexes other than those containing barium were found to fragment into homometallic species.
Bis(phenylethynyl)ytterbium - a novel organolanthanide.
Publisher: Elsevier BV
Date: 02-1978
Structures and thermal decomposition of some diphenyllead bispolyfluorobenzoates
Publisher: CSIRO Publishing
Date: 1974
DOI: 10.1071/CH9741895
Abstract: The diphenyllead bispolyfluorobenzoates, Ph2Pb(O2CR)2 (R = C6F5, p-MeOC6F4 or p-EtOC6F4), obtained from diphenyllead diacetate and the appropriate polyfluorobenzoic acids, are considered to have associated structures with bridging bidentate carboxylate groups in the solid state and to be predominantly monomeric with chelating carboxylate groups at low concentrations in chloroform. Thermal decomposition of Ph2Pb(O2CC6F5)2 in boiling pyridine gave Ph2Pb(C6F5)2 and a low yield of Ph3PbC6F5, whereas Ph2Pb(O2C-p-MeOC6F4)2 and Ph2Pb(O2C-p-EtOC6F4)2 gave low yields of Ph3Pb-p-MeOC6F4 and Ph2Pb(p-EtOC6F4)2 respectively. From decomposition of Ph2Pb(O2CC6F5)2 under vacuum, Ph2Pb(C6F5)2, Ph3PbC6F5, Ph4Pb, PhC6F5, (C6F5)2CO and CO2 were obtained, whilst Ph4Pb, Ph2, PhR, RCO2Ph, R2CO and CO2 were detected from pyrolysis of Ph2Pb(O2CR)2 (R= p-MeOC6F4 or p-EtOC6F4). These compounds are formed by competing decarboxylation, rearrangement, and (under vacuum) homolysis reactions of the diorganolead dicarboxylates, and by further reactions of the rearrangement products.
Some reactions of phenylene-and polyphenylene-mercurials
Publisher: Elsevier BV
Date: 11-1986
Novel Heterobimetallic Neodymium/Calcium 8‐Quinolinolate Complexes Prepared Directly From the Metals
Publisher: Wiley
Date: 31-08-2004
Cover Feature: Direct Reaction – One Step Route to Synthesize Lanthanoid‐iodide Formamidinates (Chem. Asian J. 14/2023)
Publisher: Wiley
Date: 14-06-2023
Organolanthanoids. III. Preparations and properties of some Di(alkynyl)lanthanoids
Publisher: CSIRO Publishing
Date: 1982
DOI: 10.1071/CH9820941
Abstract: From reactions between di(alkynyl)mercurials and lanthanoid elements in tetrahydrofuran or 1,2-dimethoxyethane, the organolanthanoids (PhCC)2Yb and (PhCC)2Eu(thf)0.25 (thf = tetrahydrofuran) have been isolated, and (RCC)2M (R = Ph or But, M = Yb R = Ph, M = Eu) characterized in solution. Bis(phenylethynyl)ytterbium has also been obtained by ligand exchange between (C6F5)2Yb or (ButCC)2Y and phenylacetylene. The di(alkynyl)lanthanoids are considered to have associated structures with bridging alkynyl groups. Hydrolysis of (RCC)2M derivatives yields acetylenes RCCH, together with alkenes RCHCH2 (greater for M = Yb than M = Eu), and, when M = Yb, R = Ph, a little ethylbenzene.
Near‐Infrared Electrochemiluminescence from Bistridentate Ruthenium(II) Di(quinoline‐8‐yl)pyridine Complexes in Aqueous Media
Publisher: Wiley
Date: 02-2020
Facile Reversible Benzophenone Insertion into Rare‐Earth Metal Pyrazolate Complexes
Publisher: Wiley
Date: 31-07-2017
Diverse Heteroleptic Ytterbium(III) Thiocyanate Complexes by Oxidation from Bis(thiocyanato)ytterbium(II)
Publisher: Wiley
Date: 17-04-2001
DOI: 10.1002/1521-3765(20010417)7:8<1784::AID-CHEM17840>3.0.CO;2-7
Abstract: The new ytterbium(II) thiocyanate complex [Yb(NCS)2(thf)2] (1), synthesised by redox transmetallation between [Hg(SCN)2] and ytterbium metal in THF at room temperature, gave monomeric, eight coordinate [Yb-(NCS)2(dme)3] (2, dme = 1,2-dimethoxyethane) on crystallisation from DME, and is a powerful, synthetically useful reductant. Thus, oxidation of 1 with Hg(SCN)2, Hg(C6F5)2/HOdpp (HOdpp = 2,6-diphenylphenol), TlCp (Cp = C5H5 or CH3C5H4), Tl(Ph2pz) (Ph2pz = 3,5-diphenylpyrazolate) and CCl3CCl3 in THF yielded the ytterbium(II) complexes [Yb(NCS)3(thf)4] (3), [Yb-(NCS)2(Odpp)(thf)3](4), [Yb(NCS)2Cp-(thf)3] (Cp = C5H5 (5), CH3C5H4 (6)), [Yb(NCS)2(Ph2pz)(thf)4] (7) and [Yb(NCS)2Cl(thf)4] (8). In the solid state, complexes 4, 6 and 7 were shown by X-ray crystallography to be six, eight and eight coordinate monomers, respectively. Exclusively terminal, N-bound transoid thiocyanate bonding is observed with eta1-Odpp (4), eta5/-C5H4Me (6) and eta2-Ph2Pz (7) ligands attached approximately perpendicular to the N...N vector. The chloride complex 8 is not a molecular species, but consists of discrete, seven coordinate [YbCl2(thf)5] cations and [Yb(NCS)4(thf)3] anions. By contrast, oxidation of 1 with TlO2CPh gave a mixture of [[Yb(NCS)-(O2CPh)2(thf)2]2] (9) and 3 through rearrangement of an initially formed [Yb(NCS)2(O2CPh)] species. The X-ray structure of 9 indicates a dimeric complex with a (Yb(mu-O2CPh)4Yb] core that contains both bridging bidentate and bridging tridentate benzoate groups, and with a terminal N-bound thiocyanate and two THF ligands on each ytterbium. Reduction of Ph2CO with 1 in THF yielded the dinuclear complex [[Yb(NCS)2(thf)3]2(mu-OC(Ph)2C(Ph)2O)] (10), in which two octahedral Yb centres are bridged by a 1,1,2,2-tetraphenylethane-1,2-diolate ligand, derived from reductive coupling of the benzophenone reagent.
The vibrational spectra of some tetraalkylphosphonium ions
Publisher: CSIRO Publishing
Date: 1967
DOI: 10.1071/CH9670583
BiPh3—A convenient synthon for heavy alkaline-earth metal amides
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B806948D
Abstract: Environmentally friendly, commercially available BiPh3 reacts with heavy alkaline-earth metals (Ae) and bulky trimethylsilylamines to give the corresponding amides [Ae{N(SiMe3)(R)}2(thf)n] (R=SiMe3, 2,4,6-Me3C6H2, 2,6-iPr2C6H3) in good yields, providing proof of concept for a general synthetic method.
Very facile decarboxylation syntheses of polymethoxyphenylmercury compounds
Publisher: Elsevier BV
Date: 07-1982
Trinuclear and tetranuclear manganese clusters derived from cyano(imino(methoxy)methyl)nitrosomethanide (cmnm)
Publisher: Elsevier BV
Date: 03-2013
Preparation and properties of some triphenyllead carboxylates
Publisher: CSIRO Publishing
Date: 1970
DOI: 10.1071/CH9701359
Abstract: The triphenyllead carboxylates, Ph3PbO2CR (R = C6F5, 4-MeOC6F4, 4- EtOC6F4, 2,4-(NO2)2C6H3, or C6Cl5) have been obtained by reactions of triphenyllead acetate with the appropriate carboxylic acids. The first four compounds are monomeric with unidentate carboxylate coordination in chloroform, and all are probably polymeric with bridging carboxylate groups in the solid state. The compounds, Ph3PbO2CR (R = C6F5, 4-RieOC6F4, or 4-EtOC6F4), undergo decarboxylation in boiling pyridine to give the corresponding polyfluoroaryltriphenyllead derivatives, but the other carboxylates do not decompose in a similar manner. The phenylmercuric carboxylates, PhHgO2CR (R = 4-MeOC6F4 or 4-EtOC6F4), have also been prepared and shown to decarboxylate to the corresponding 4-alkoxytetrafluorophenylphenylmercurials. Cleavage of the compounds, Ph3PbR (R = C5F6 or 4-1MeOC6F4), with pentafluorobenzoic acid yields diphenyllead bispentafluorobenzoate.
Novel Mercury Phosphanylamides
Publisher: Wiley
Date: 03-2005
Synthesis and Structural Properties of Anhydrous Rare Earth Cinnamates, [RE(cinn)3]
Publisher: Wiley
Date: 30-11-2007
The nature of sulphinate coordination in zinc and cadmium arenesulphinates
Publisher: Elsevier BV
Date: 08-1969
Organoamidometallics. V. Syntheses of [N,N-diethyl-N'-polyfluorophenyl-ethane-1,2-diaminato(1-)]platinum(II) Complexes by Decarboxylation Reactions, and the X-Ray Crystal Structure of trans-[Pt(NC6F5C
Publisher: CSIRO Publishing
Date: 1991
DOI: 10.1071/CH9911669
Abstract: From reactions between PtX2( deen ) (X=I, Br or Cl deen = N,N-diethylethane-1,2-diamine), thallous pentafluorobenzoate or 2,3,5,6-tetrafluorobenzoate, and the appropriate polyfluorobenzene in pyridine (py) or 4-methylpyridine ( mepy ), the organoamidoplatinum (II) complexes [Pt(NRCH2CH2Net2)X(L)](R = p-HC6F4 or C6F5, X = 1, Br or Cl , L = py R = p-HC6F4, X = I, L = mepy R = p-MeC6F4 or p-IC6F4, X = I, L = py R = 2,3,5-F3C6H2, X = Br, L = py) have been prepared. The X-ray crystal structure of [Pt(NC6F5CH2CH2Net2)I(py)](triclinic, space group Pī (No. 2), a 9.308(1), b 9.615(2), C 11.143(2)Ǻ, α 88.70(2),β 88.58(1), γ 89.60(2)°, R 0.0518, Rw 0.0704 for 3237 observed reflections) shows the complex to have square planar stereo-chemistry with py trans to NEt2 and NC6F5 trans to iodine. The stereochemistry of the amido nitrogen approaches triangular (sum of angles 353°) and the N-C6F5 bond has partial double-bond character. Surprisingly, the ethyl substituents have a configuration in which the methyl groups are orientated back towards platinum. Other [Pt(NRCH2CH2Net2)X(L)] complexes are considered to have similar stereochemistry on the basis of comparison of spectroscopic data, particularly 3JPt,H(py) and 3JPt,H(CH2) coupling constants.
Dimethyltin(IV) Bis(3,5‐diphenylpyrazolate) as a Synthetic Reagent in the Preparation of Rare‐Earth Pyrazolate Complexes
Publisher: Wiley
Date: 10-2008
Can Bismuth Replace Mercury in Redox Transmetallation/Protolysis Syntheses from Free Lanthanoid Metals?
Publisher: Wiley
Date: 14-11-2018
Abstract: Tris(pentafluorophenyl)bismuth has been examined as a potential replacement for diarylmercurials in redox transmetallation rotolysis (RTP) syntheses of reactive rare earth compounds from free rare earth metals, HgAr
Electrochemical, spectroelectrochemical and theoretical studies on the reduction and deprotonation of the photovoltaic sensitizer [(H3-tctpy)RuII(NCS)3]− (H3-tctpy=2,2′:6′,2′′-terpyridine-4,4′,4′′-tri
Publisher: Elsevier BV
Date: 08-2000
Pushing the Boundary of Covalency in Lanthanoid‐Tellurium Bonds: Insights from the Synthesis, Molecular and Electronic Structures of Low‐Coordinate, Monomeric Europium(II) and Ytterbium(II) Tellurolat
Publisher: Wiley
Date: 21-06-2023
Abstract: Owing to the strict hard/soft dichotomy between the lanthanoids and tellurium atoms, and the strong affinity of lanthanoid ions for high coordination numbers, low‐coordinate, monomeric lanthanoid tellurolate complexes have remained elusive as compared to the lanthanoid complexes with lighter group 16 elements (O, S, and Se). This makes the development of suitable ligand systems for low‐coordinate, monomeric lanthanoid tellurolate complexes an appealing endeavor. In a first report, a series of low‐coordinate, monomeric lanthanoid (Yb, Eu) tellurolate complexes were synthesized by utilizing hybrid organotellurolate ligands containing N‐donor pendant arms. The reaction of bis[2‐((dimethylamino)methyl)phenyl] ditelluride, 1 and 8,8′diquinolinyl ditelluride, 2 with Ln 0 metals ( Ln =Eu, Yb) resulted in the formation of monomeric complexes [ Ln II (TeR) 2 (Solv) 2 ] [R=C 6 H 4 ‐2‐CH 2 NMe 2 ] [ 3 : Ln =Eu, Solv=tetrahydrofuran 4 : Ln =Eu, Solv=acetonitrile 5 : Ln =Yb, Solv=tetrahydrofuran 6 : Ln =Yb, Solv=pyridine] and [Eu II (TeNC 9 H 6 ) 2 (Solv) n ] ( 7 : Solv=tetrahydrofuran, n=3 8 : Solv=1,2‐dimethoxyethane, n=2), respectively. Complexes 3 – 4 and 7 – 8 represent the first sets of ex les of monomeric europium tellurolate complexes. The molecular structures of complexes 3 – 8 are validated by single–crystal X‐ray diffraction studies. The electronic structures of these complexes were investigated using Density Functional Theory (DFT) calculations, which revealed appreciable covalency between the tellurolate ligands and lanthanoids.
Selective removal of ortho halogens by a diorganolanthanoid
Publisher: Elsevier BV
Date: 1984
Organothallium compounds. IV. Carboxylatobis(pentafluorophenyl)thallium(III) compounds and their complexes with 1,10-phenanthroline and 2,3'-bipyridyl
Publisher: CSIRO Publishing
Date: 1967
DOI: 10.1071/CH9670459
Abstract: Carboxylatobis(pentafluorophenyl)thallium(III) compounds, Tl(OCOR)(C6F5)2 (R = Ph, Me, or C6F5), have been prepared by a metathesis reaction between bromobis(pentafluorophenyl)thallium(III) and the appropriate sodium or ammonium carboxylate in aqueous ethanol. They are considered to have dimeric structures with bridging carboxylate groups. With 1,10- phenanthroline (phen), the complexes Tl(OCOR)(C6F5)2 phen, which are monomeric in benzene and acetone, are obtained. The complexes, Tl(OCOR)(C6F6)2 bipy (bipy = 2,2'-bipyridyl R = Ph or Me) can be prepared only by using excess ligand. They decompose to Tl(OCOR)(C6F5)2 compounds on attempted recrystallization, partly dissociate into Tl(OCOR)(C6F5)2 and bipyridyl in benzene and acetone, and undergo ligand exchange with 1,10-phenanthroline to give Tl(OCOR)(C6F5)2 phen complexes. By contrast, Tl(OCOC6F5)-(C6F5)2 bipy has been prepared without using excess ligand and can be recrystallized unchanged. It is monomeric in benzene, but dissociates slightly in acetone. The complexes, Tl(OCOR)(C6F5)2(phen or bipy), are considered to contain five-coordinate thallium.
The X-ray crystal structure of Hg(C6 H4 OMe-4)(C 6 F5 ): An unexpected twist
Publisher: Springer Science and Business Media LLC
Date: 2003
ATR-FTIR spectroscopy shows changes in ovarian cancer cells after incubation with novel organoamidoplatinum(ii ) complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8AN01558A
Abstract: ATR-FTIR spectroscopy has been applied to compare the effect of new organoamidoplatinum( ii ) complexes with cisplatin on cells from a cisplatin-sensitive and a cisplatin-resistant ovarian cancer cell line.
The nature of the surface film on steel treated with cerium and lanthanum cinnamate based corrosion inhibitors
Publisher: Elsevier BV
Date: 02-2006
Structurally diverse organoamides and organoamido-, organometallic-lithium aggregates from reactions of N-(2-phenoxyphenyl)-N-(trimethylsilyl)amine with LiBun†
Publisher: Royal Society of Chemistry (RSC)
Date: 2001
DOI: 10.1039/B103642B
Influence of Praseodymium
Publisher: The Electrochemical Society
Date: 2007
DOI: 10.1149/1.2790724
Redox transmetallation approaches to the synthesis of extremely bulky amido-lanthanoid(ii ) and -calcium(ii ) complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8DT02138D
Abstract: Redox transmetallation protolysis and direct redox transmetallation reactions have been employed to access a variety of extremely bulky amido-lanthanoid( ii ), and related calcium( ii ) complexes which cannot be prepared using classical salt metathesis pathways.
Designed Synthesis of Mononuclear Tris(heteroleptic) Ruthenium Complexes Containing Bidentate Polypyridyl Ligands
Publisher: American Chemical Society (ACS)
Date: 11-1995
DOI: 10.1021/IC00128A028
The effects of light lanthanoid elements (La, Ce, Nd) on (Ar)CF–Ln coordination and C–F activation in N,N-dialkyl-N′-2,3,5,6-tetrafluorophenylethane-1,2-diaminate complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT30604B
Abstract: A new class of homoleptic organoamido rare earth complexes [Ln(L(Me) or L(Et))(3)] (Ln = La, Ce, Nd L(Me/Et) = p-HC(6)F(4)N(CH(2))(2)NMe(2)/Et(2)) exhibiting (Ar)CF-Ln interactions has been isolated from redox-transmetallation rotolysis (RTP) reactions between the free metals, Hg(C(6)F(5))(2) and L(Me/Et)H in tetrahydrofuran, together with low yields of [Ln(L(Me))(2)F](3) (Ln = La, Ce) or [Nd(L(Et))(2)F](2) species, resulting from C-F activation reactions. The structures of the homoleptic complexes have eight-coordinate Ln metals with two tridentate (N,N',F) amide ligands including (Ar)CF-Ln bonds and either a bidentate (N,F) ligand (Ln = La, Ce, Nd L(Et)) or a bidentate (N,N') ligand (Ln = Nd L(Me)), in an unusual case of linkage variation. All (Ar)CF-Ln bond lengths are shorter than or similar to the corresponding Ln-NMe(2)/Et(2) bond lengths. In [Ln(L(Me))(2)F](3) (Ln = La, Ce) complexes, there is a six-membered ring framework with alternating F and Ln atoms and the metal atoms are eight-coordinate with two tridentate (N,N',F) L(Me) ligands, whilst [Nd(L(Et))(2)F](2) is a fluoride-bridged dimer.
The X-ray crystal structures of three bis(cyclopentadienyl)titanium(IV) derivatives
Publisher: Springer Science and Business Media LLC
Date: 08-02-2006
Small Steric Variations in Ligands with Large Synthetic and Structural Consequences
Publisher: Wiley
Date: 21-01-2008
Activity and DNA binding of new organoamidoplatinum (II) complexes
Publisher: Springer Science and Business Media LLC
Date: 02-1999
Abstract: Two series of organoamidoplatinum (II) complexes were synthesized [Class 1, Pt(NRCH2)2L2 and Class 2, Pt(NRCH2CH2NR2')L(X)] and their antitumour activity examined by a range of in vitro, cellular and animal studies. All Class 1 compounds exhibited activity comparable to cisplatin in mouse leukemia L1210 cells, but were at least 8-fold more active against the cisplatin-resistant L1210/R line. The lead compound 1a (R=p-HC6F4) caused nearly complete tumour regression in the ADJ/PC6 mouse tumour model. Compound 1a exhibited similar DNA reactivity to cisplatin, resulting in virtually identical DNA sequence specificity as cisplatin, and had similar time and concentration dependency of interstrand crosslinks. Compared with cisplatin, la showed 3-fold greater cellular uptake into human ovarian carcinoma 2008 cells, and this was dramatically enhanced to 17-fold in the cisplatin-resistant 2008/R line. The activity of 1a, therefore, appears to be due at least in part to a greater cellular uptake into tumour cells, particularly cisplatin-resistant cells, and once in the cell it reacts with DNA in a similar manner to that of cisplatin. The enhanced uptake and enhanced cytotoxicity of Class 1 compounds, and 1a in particular, may be due to a greater hydrophobicity compared with cisplatin. The activity of the Class 2 compounds, especially in the cisplatin-resistant cell lines, is unusual because they have trans amine ligands, and further study of both classes of compounds is warranted.
Trinuclear and Mononuclear Lanthanoid Complexes Containing 2‐Methyl‐8‐quinolinolate: Synthesis, Structures, and Magnetic Properties
Publisher: Wiley
Date: 21-05-2019
Organoindium compounds. II. Some coordination derivatives of trispentafluorophenylindium
Publisher: CSIRO Publishing
Date: 1972
DOI: 10.1071/CH9721169
Abstract: The complexes (C6F5In,L [L = pyridine (py), Ph3P, Ph3PO, Ph3AsO, or N,N,N?,N'-tetramethylethylenediamine (tmed)], (CeF5)31n(OSMe2)2, and [(C6F5)3)aIn]2bipy (bipy = 2,2'-bipyridyl) have been prepared by reaction of (C6F5)3In,diox (diox = 1,4-dioxan) with the appropriate ligands, and (C6F5)31n,AsPh3,( C6F5)3 (THF)2 (THF = tetrahydrofuran), and (C6F5)31n]2(Ph2PCH2)2 have been similarly obtained from (C6F5)3In,OEt2. Monomeric structures with four-coordinate indium are proposed for the complexes (C6F5)3In,L (L = py, Ph3P, Ph3As, Ph3PO,or Ph3AsO), and monomeric five-coordinate structures for the complexes (C6F5)31n(L)2 (L = Me2SO or THF). The derivatives [(C6F5)31n]2L [L = bipy or (Ph2PCH2)2] and (C6F5)3In,tmed are considered to have bridging ligands with four- and five- coordinate indium respectively.
Two New Benzoate‐di(methylcyclopentadienyl)ytterbium(III) Complexes: [Yb(MeCp)2(O2CC6F5)]2 and [Yb(MeCp)2(O2C‐o‐HC
Publisher:
Wiley
Date:
25-03-2003
Publisher: Wiley
Date: 25-03-2003
The synthesis and X-ray crystal structures of rare earth(III) perfluoroadipate complexes — Novel coordination polymers
Publisher: Canadian Science Publishing
Date: 2009
DOI: 10.1139/V08-104
Abstract: A representative series of polymeric hydrated lanthanoid perfluoroadipates [Ln 2 (pfad) 3 (H 2 O) n ]·mH 2 O (Ln = La, Ce, Nd, Gd, Yb) has been prepared from the reaction of perfluoroadipic acid with either the appropriate lanthanoid oxide or Ce 2 (CO 3 ) 3 in water. X-ray crystal structures showed [Ln 2 (pfad) 3 (H 2 O) 10 ]·4H 2 O (La, Nd) to be two-dimensional inorganic polymers, which contain nine-coordinate Ln atoms to which are attached five water molecules and four carboxylate oxygen atoms. Two pfad ligands bridge two Ln atoms through one carboxylate group, the other being free, whilst one pfad ligand bridges four Ln atoms in a µ 4 -(η 1 ,η 1 /η 1 ,η 1 ) manner. In two-dimensional polymeric [Yb 2 (pfad) 2 (H 2 O) 8 ](pfad)·6H 2 O, each eight-coordinate ytterbium atom has four water ligands and four carboxylate oxygen donor atoms. The two carboxylate ligands bind in a µ 4 -(η 1 ,η 1 /η 1 ,η 1 ) manner, and there is one pfad counter-ion per two ytterbium atoms. These structures show features quite different from those of many lanthanoid adipate complexes [Ln 2 (ad) 3 (H 2 O) n ]·mH 2 O, but there is no F-Ln coordination. From the reaction of [Nd 2 (pfad) 3 (H 2 O) 10 ]·4H 2 O with benzene-1,2-disulfonic acid (H 2 bds), the mixed ligand complex [Nd 2 (bds) 2 (pfad)(H 2 O) 8 ] was isolated. This is a one-dimensional polymer featuring Nd 2 (bds) 2 units linked together by µ-η 2 ,η 2 pfad ligands. Each Nd atom is nine-coordinate with three sulfonate oxygen donors, two carboxylate oxygen atoms, and four water ligands, and the bds ligands bind in the new µ-η 2 (O,O′),η 1 (O′′) manner for Ln complexes. Surprisingly, [Na 2 pfad] was isolated unhydrated from water, the six-coordinate Na atoms being coordinated by four carboxylate oxygen atoms and two (C)-F atoms in an octahedral array. The ligands are duodecadentate, each –CF 2 CO 2 unit binding to five different sodium ions through four oxygen and one α-F atom with the second α-F atom bound to a sodium ion in a OC(O)CF-Na chelate ring.Key words: rare earths, lanthanoid, X-ray crystal structures, adipates, carboxylates.
New, environmentally friendly, rare earth carboxylate corrosion inhibitors for mild steel
Publisher: Elsevier BV
Date: 07-2018
Syntheses at Elevated Temperature and Structures of Lanthanoid/Alkaline Earth Heterobimetallic Derivatives of 2‐Methyl‐8‐hydroxyquinoline
Publisher: Wiley
Date: 06-2010
Abstract: Rearrangement reactions between Ln(MQ) 3 and AE(MQ) 2 (MQ = 8‐quinaldinolate) at 200–300 °C in a 1,2,4,5‐tetramethylbenzene (TMB) flux afforded the homoleptic heterobimetallic complexes [Ln 2 AE(MQ) 8 ] (Ln = Eu, Gd, Tb, Er with AE = Mg Ln = La, Eu with AE = Ca) and [Eu 3 Ba(MQ) 11 ] · 2TMB. From an attempt to prepare [La 2 Mg(MQ) 8 ], [Mg 4 (MQ) 8 ] was isolated, and it was also obtained with the heterobimetallics from syntheses in which Ln = Eu, Gd, Tb. Surprisingly, [Er 3 (MQ) 7 CO 3 ] was isolated from an attempted synthesis of [Er 2 Ca(MQ) 8 ], and the Eu analogue was prepared from Eu(MQ) 3 and CaCO 3 in TMB at 210 °C. The [Ln 2 AE(MQ) 8 ] complexes have a trinuclear structure with a linear or nearly linear Ln–AE–Ln array. Octacoordinate Ln atoms have one terminal chelating (N, O) MQ ligand and three chelating‐bridging MQ ligands that link to AE through the phenolic oxygen atoms, leading to hexacoordination of AE. In [Eu 3 Ba(MQ) 11 ] · 2TMB, an Eu atom is positioned above the Ba–Eu vector of a somewhat bent Eu–Ba–Eu unit. All atoms are octacoordinate, and the structure features μ 3 ‐η 2 (N,O):η 1 (O):η 1 (O) MQ ligands in addition to terminal chelating and chelating‐bridging μ‐η 2 (N,O):η 1 (O) MQ groups observed in [Ln 2 AE(MQ) 8 ] complexes. The three modes of ligation are also observed in [Mg 4 (MQ) 8 ] where Mg is hexacoordinate but with two different arrays. [Ln 3 (MQ) 7 CO 3 ] complexes have a perpendicular Ln–Ln–Ln arrangement with two octacoordinate metal atoms flanking a heptacoordinate one. Carbonate binding features the new η 1 (O)‐μ 3 ‐η 1 (O′):η 1 (O′):η 1 (O′)‐η 1 (O″) ligation mode. The carbonate ligand chelates to each of the outer Ln atoms, which are also linked to one chelating and two chelating‐bridging MQ ligands. Attached to the central Ln atom is a carbonate oxygen atom, four oxygen atoms from chelating‐bridging MQ ligands and a terminal MQ chelate.
S-Sulphinates of cobalt(III) planar chelates and sulphur dioxide insertion into a cobalt(III)-carbon bond
Publisher: CSIRO Publishing
Date: 1970
DOI: 10.1071/CH9700481
Abstract: The reactivity of the cobalt-carbon bond towards sulphur dioxide has been investigated in the compounds Rco111(L)B where L = N,N'-ethylenebis(salicyl-aldiminato), N,N'-phenylenebis(salicylaldiminato), or bis(dimethylg1yoximato) B = water or pyridine. In the Schiff base complexes, for R = alkyl, insertion into the cobalt-carbon bond proceeds smoothly to give the corresponding sulphinato derivatives. Reaction also occurs with methylcobaloxime and a pentafluorobenzene- cobalt-Schiff base compound, but the products are not so well defined. There is no reaction with cobalt-aryl bonds for any of the chelates. The alkane- and arene- sulphinato complexes can be synthesized by an alternative oxidative-addition reaction NaCOL+RSO2Cl or a replacement reaction XCoL+AgSO2R or NaSO2R (X = Cl,I). The infrared spectra of the complexes show that the sulphinato group is bonded in the manner shown: (See diagram in article) The p.m.r. spectra of the complexes are discussed in some detail. Reactions of the sulphinato derivatives with donor molecules and the halogens are briefly described.
RE(III) 3-Furoate Complexes: Synthesis, Structure, and Corrosion Inhibiting Properties
Publisher: MDPI AG
Date: 13-12-2022
DOI: 10.3390/MOLECULES27248836
Abstract: In this study, two types of Rare Earth (RE) 3-furoate complexes were synthesized by metathesis reactions between RE chlorides or nitrates and preformed sodium 3-furoate. Two different structural motifs were identified as Type 1RE and Type 2RE. The Type 1RE monometallic complexes form 2D polymeric networks with the composition [RE(3fur)3(H2O)2]n (1RE = 1La, 1Ce, 1Pr, 1Nd, 1Gd, 1Dy, 1Ho, 1Y 3furH = 3-furoic acid) while Type 2RE bimetallic complexes form 3D polymeric systems [NaRE(3fur)4]n (2RE = 2Ho, 2Y, 2Er, 2Yb, 2Lu). The stoichiometric mole ratio used (RE: Na(3fur) = 1:3 or 1:4) in the metathesis reaction determines whether 1RE or 2RE (RE = Ho or Y) is formed, but 2RE (RE = Er, Yb, Lu) were obtained regardless of the ratio. The corrosion inhibition behaviour of the compounds has been examined using immersion studies and electrochemical measurements on AS1020 mild steel surfaces by a 0.01 M NaCl medium. Immersion test results revealed that [Y(3fur)3(H2O)2]n has the highest corrosion inhibition capability with 90% resistance after 168 h of immersion. Potentiodynamic polarisation (PP) measurements also indicate the dominant behaviour of the 1Y compound, and the PP curves show that these rare earth carboxylate compounds act predominantly as anodic inhibitors.
New aspects of thallation
Publisher: Elsevier BV
Date: 07-1976
Synthesis, Characterization, and Theoretical Studies of cis-Dichloridobis(8-quinolinethiolato)tin(IV) and bis(8-Sulfanylquinolinium) Hexachloridostannate(IV) Derivatives
Publisher: CSIRO Publishing
Date: 2020
DOI: 10.1071/CH19561
Abstract: The structural characterisation of bis(8-sulfanylquinolinium) hexachloridostannate(iv) (2) is reported and the variable reaction behaviour of this compound in different solvents has been explored. In particular, attempted recrystallization of 2 from chloroform and dichloromethane affords two polymorphs of cis-dichloridobis(8-quinolinethiolato)tin(iv), 3m and 3t, respectively. Attempted recrystallization of 2 from methanol gives crystals of 8,8′-dithiodiquinolinium hexachloridostannate(iv) 4. When 2 is dissolved in dimethyl sulfoxide in the presence of air, it undergoes oxidation to afford diquinolinyl-8,8′-disulfide 5. The molecular structures of the isolated compounds 2–4 are unambiguously authenticated by single crystal X-ray diffraction studies. The electronic structure properties of all the isolated compounds 2–4 are thoroughly studied by DFT calculations.
Direct reaction of iodine-activated lanthanoid metals with 2,6-diisopropylphenol
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT11752E
Abstract: Rare earth metals activated with ca. 2% iodine react directly with 2,6-diisopropylphenol (HOdip) in tetrahydrofuran (thf), 1,2-dimethoxyethane (dme), and dig-dme (dig = di(2-methoxyethyl) ether) to give solvated phenolate complexes [Ln(Odip)(3)(thf)(n)] (Ln = La, Nd, n = 3 Ln = Sm, Dy, Y, Yb, n = 2), [Eu(Odip)(μ-Odip)(thf)(2)](2), [Ln(Odip)(3)(dme)(2)] (Ln = La, Yb) and [La(Odip)(3)(dig)] in good yield for Ln = La, Nd, Eu but modest yield for smaller Ln metals under comparable conditions. However, increasing the excess of metal greatly increased the yield for Ln = Y. The synthetic method has general potential, at least for lanthanoid phenolates. Comparison redox transmetallation rotolysis (RTP) reactions between Ln metals, Hg(C(6)F(5))(2) and the phenol gave higher yields in shorter time and, for Eu, gave [Eu(Odip)(3)(thf)(3)] in contrast to an Eu(II) complex from Eu(I(2)). New [Ln(Odip)(3)(thf)(3)] complexes have fac-octahedral structures and [Ln(Odip)(3)(thf)(2)] monomeric five coordinate distorted trigonal bipyramidal structures with apical thf ligands. [Eu(Odip)(μ-Odip)(thf)(2)](2) is an unsymmetrical dimer with two bridging Odip ligands. One five coordinate Eu atom has distorted trigonal bipyramidal stereochemistry and the other is distorted square pyramidal. Whilst [La(Odip)(3)(dme)(2)] has irregular seven coordination with mer-Odip and chelating dme ligands, [Ln(Odip)(3)(dme)(2)] (Ln = Dy, Y (prepared by ligand exchange), Yb) are monomeric six coordinate with one chelating and one unidentate dme. A six coordinate fac-octahedral arrangement is observed in [La(Odip)(3)(dig)].
The formation and thermal decomposition of some alkyl- and acetyl-manganesecarbonyl complexes with dialkyltellurium ligands
Publisher: Elsevier BV
Date: 08-1994
The structure of di-μ-pentafluorobenzoatobis[bis(pentafluorophenyl)(triphenylphosphine oxide)thallium(iii)]
Publisher: Elsevier BV
Date: 1981
Organoamido- and Aryloxo-Lanthanoids. I. The Preparation and Characterization of Some Lanthanoid(II) Organoamides, and the X-Ray Crystal Structure of cis-Bis(Carbazol-9-Yl)Tetrakis(tetrahydrofuran)eur
Publisher: CSIRO Publishing
Date: 1990
DOI: 10.1071/CH9900795
Abstract: Reaction of carbazole ( Hcbz ) or 2-phenylindole ( Hpin ) with bis ( pentafluorophenyl )-ytterbium or -europium in tetrahydrofuran ( thf ) gives the complexes M( cbz )2( thf )4 (M = Yb or Eu ) or Yb (pin)2( thf )4. From treatment of lanthanoid metals with bis ( pentafluorophenyl )mercury and 2-phenylindole, 2,3,4,5-tetraphenylpyrrole ( Htpp ) or carbazole , the complexes M(pin)2( thf )4 (M = Yb , Eu or Sm ), M( tpp )2( thf )3 (M = Yb or Sm ) and Yb ( cbz )2( thf )4 have been isolated. Desolvation of M(pin)2( thf )4 under vacuum yields Yb (pin)2( thf ) and Sm (pin)2( thf )3. Oxidation of Sm (pin)2( thf )4 with Hg(C6F5)2 and 2-phenylindole gives Sm (pin)3( thf ). The crystal structure of Eu ( cbz )2( thf )4 shows the complex to be monomeric with distorted octahedral stereochemistry for europium, cis-carbazol-9-yl ligands ({ Eu -N} 2.559 Ǻ), and longer Eu -O bonds (av. 2.600Ǻ) trans to N than mutually trans ({ Eu -O} 2.553Ǻ). Other complexes M(NR2)2( thf )n (NR2 = pin, cbz or tpp ) are considered to be monomeric with five (n = 3) or six (n = 4) coordination.
Anion–Anion Interactions in the Crystal Packing of Functionalized Methanide Anions: An Experimental and Computational Study
Publisher: American Chemical Society (ACS)
Date: 19-03-2014
DOI: 10.1021/CG500051M
Intramolecular Metal–Fluorocarbon Coordination, CF Bond Activation and Lanthanoid–Fluoride Clusters with Tethered Polyfluorophenylamide Ligands
Publisher: Wiley
Date: 06-03-2009
Abstract: Activating C--F bonds: Strong metal-fluorocarbon coordination in complexes of electropositive metals (e.g., Na, K, Yb) with chelating polyfluorophenyl-substituted amide ligands is a precursor to C--F bond activation and fluoride abstraction when M=Yb(II), giving heteroleptic Yb(III) fluoride clusters (see scheme).Metalation of either N,N-diethyl- or N,N-dimethyl-N'-2,3,5,6-tetrafluorophenylethane-1,2-diamines (HL 1 a, 1 b respectively) with [M{N(SiMe(3))(2)}] (M=Na, K) or [Yb{N(SiMe(3))(2)}(2)(thf)(2)] yielded the metal-amido compounds [Na(L)] (2 a), [K(L)] (3 a) and [Yb(L)(2)(thf)(2)] (4 a, 4 b). The Yb complexes were also synthesised by redox transmetalation/ligand exchange from Yb, Hg(C(6)F(5))(2) and HL in THF or 4 a from a reaction of 3 a with YbI(2) in THF. In the presence of N,N,N',N'- tetramethyl-1,2-ethanediamine (TMEDA) the complexes 2 a and 3 a yielded [Na(L)(2)Na(tmeda)] (5 a) and [K(2)(L)(2)(tmeda)(2)] (6 a), respectively, as crystalline compounds, whilst crystallisation of 4 a from DME gave [Yb(L)(2)(dme)] (7 a). Their structures have chelating metal-amide and NR(2) donors and additional intramolecular M-F-C connectivity with relatively short bond lengths (Na--F 2.65-3.00 A K--F 2.70-3.00 A Yb--F 2.56 A). The Yb complexes undergo C--F activation in solution forming [Yb(4)(L)(6)F(6)] (8 a, 8 b). The connectivity of [Yb(4)(L)(6)F(6)], as shown by the X-ray structures, comprised a circular Yb(4)(mu-F)(4) periphery with two opposing Yb centres having either one L ligand and a Yb(2)(mu-F)(2) bridge or two L ligands. Each polyfluorophenylamide exhibits additional intramolecular Yb-F-C coordination from one of the ortho-F atoms resulting in seven or eight coordinate Yb centres. An attempt to synthesise 4 a by redox transmetalation/ligand exchange using Hg(C[triple chemical bond]CPh)(2) as the mercury reagent gave [Yb(4)(O)(2)(L)(4)(C[triple chemical bond]CPh)(4)(thf)(2)]THF (9 aTHF), most likely as a result of oxidation of the initially formed product.
Developments in Heterobimetallic s-Block Systems: Synthesis and Structural Survey of Molecular M/Ae (M = Li, Na, K, Cs; Ae = Ca, Sr) Aryloxo Complexes
Publisher: American Chemical Society (ACS)
Date: 07-05-2008
DOI: 10.1021/IC702466D
Abstract: A series of novel heterobimetallic group 1/strontium and group 1/calcium aryloxo complexes having the composition [MAe(Odpp)3] [Ae=Sr and M=Na (1), K (2, 3), Cs (4) Ae=Ca and M=Na (5), K (6), Cs (7)] or [M2Ae(Odpp)4] [M=Li and Ae=Sr (9), Ca (10)] have been prepared using 2,6-diphenylphenol (HOdpp) as the ligand. Through the use of solid-state direct metalation, these compounds were obtained either directly from the reaction vessel or after workup in toluene. The Lewis base adduct [KCa(Odpp)3(thf)] (8) was obtained by treatment of [KCa(Odpp)3] (6) with tetrahydrofuran (thf). All of the compounds displayed extensive metal-pi-arene interactions, which provide significant stabilization in these reactive species. The thermal stabilities and volatilities of representative heterobimetallic strontium and calcium complexes were investigated using thermogravimetric analysis.
619. The chemistry of organothallium compounds. Part I. The preparations and properties of bis(pentafluorophenyl)thallium(III) compounds
Publisher: Royal Society of Chemistry (RSC)
Date: 1965
DOI: 10.1039/JR9650003411
Simple Syntheses, Structural Diversity, and Tishchenko Reaction Catalysis of Neutral Homoleptic Rare Earth(II orIII) 3,5-Di-tert-butylpyrazolates—The Structures of [Sc(tBu2pz)3], [Ln2(tBu2pz)6] (Ln=La
Publisher: Wiley
Date: 05-01-2001
DOI: 10.1002/1521-3765(20010105)7:1<127::AID-CHEM127>3.0.CO;2-1
Abstract: The homoleptic rare-earth pyrazolate complexes [Sc(tBu2pz)3], [Ln2(tBu2pz)6] (Ln = La, Nd, Sm, Lu), [Eu4(tBu2pz)8] and the mixed oxidation state species [Yb2(tBu2pz)5] (tBu2pz = 3,5-di-tert-butylpyrazolate) have been prepared by a simple reaction between the corresponding rare-earth metal and 3,5-di-tert-butylpyrazole, in the presence of mercury, at elevated temperatures. In addition, [Yb2(tBu2pz)6] was prepared by redox transmetallation/ligand exchange between ytterbium, diphenylmercury(II) and tBu2pzH in toluene, whilst the same reactants in toluene under different conditions or in diethyl ether gave [Yb2(tBu2pz)5]. The complexes of the trivalent lanthanoids display dimeric structures [Ln2(tBu2pz)6] (Ln = La, Nd, Yb, Lu) with chelating eta2-terminal and eta2:eta2-bridging pyrazolate coordination. The considerably smaller Sc3+ ion forms monomeric [Sc(tBu2pz)3] of putative D3h molecular symmetry, with pyrazolate ligands solely eta2-bonded. [Eu4(tBu2pz)8] is a structurally remarkable tetranuclear EuII complex with two types of europium centres in a linear array. The outer two are bonded to one terminal and two bridging pyrazolates, and the inner two are coordinated by four bridging ligands. Unprecedented mu-eta5:eta2 pyrazolate ligation is observed, with each outer Eu2+ sandwiched between two eta5-bonded pyrazolate groups, which are also eta2-linked to an inner Eu2+. The two inner Eu2+ ions are linked together by two equally occupied components of each of two symmetry related, disordered pyrazolate groups with one component eta4:eta2 bridging and one eta3:eta2 bridging. [La2(tBu2pz)6] has also been shown to be a Tishchenko reaction catalyst with several organic substrates.
Dinuclear alkynyllanthanoid(ii) dications with pentaphenylcyclopentadienyl or tri-tert-butyldiphosphacyclopentadienyl counter ions
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B514358F
Abstract: Reaction of [Yb(CpPh5)(C[triple bond]CPh)(thf)]2 (CpPh5 = pentaphenylcyclopentadienyl), prepared from Yb(C triple bond CPh)2 and HCpPh5 or Yb metal, HgPh(C[triple bond]CPh) and HCpPh5, with a controlled amount of diglyme (dig), and of Eu(C triple bond CPh)2, P triple bond CBut and dig, yield the unusual organolanthanoid(II) dicationic complexes [Yb(C[triple bond]CPh)(dig)(thf)2]2[CpPh5]2.4thf and [Eu(C triple bond CPh)(dig)2]2[P2C3But3]2 respectively.
Ionic liquids based on imidazolium, ammonium and pyrrolidinium salts of the dicyanamide anion
Publisher: Royal Society of Chemistry (RSC)
Date: 29-07-2022
DOI: 10.1039/B205641K
Synthesis, structure, and corrosion inhibiting properties of phenylacetato-rare earth(III) complexes
Publisher: Informa UK Limited
Date: 10-2020
Organolanthanides—XVI. Preparation and structure of bis(η5-cyclopentadienyl)bis(triphenylphosphine oxide)ytterbium(II)—the first X-ray crystal structure of a phosphine oxideorganolanthanide(II) comple
Publisher: Elsevier BV
Date: 1989
The Synthesis, Structures and Polymorphism of the Dimeric Trivalent Rare‐Earth 3,5‐Dimethylpyrazolate Complexes [Ln(Me2pz)3(thf)]2
Publisher: Wiley
Date: 04-04-2014
Ether-Functionalized Organoamide Coordination to Lanthanoid(II)/(III) Centres
Publisher: CSIRO Publishing
Date: 2001
DOI: 10.1071/CH01136
Four-and five-co-ordinate lanthanide (II ) aryloxides: X-ray structures of the bis(2,6-di-t-butyl-4-methylphenoxo)ytterbium(II ) complexes [Yb(OAr)2(L)2] and
Publisher: Royal Society of Chemistry (RSC)
Date: 1989
DOI: 10.1039/C39890000935
Organomercury Compounds. XVI. Thermal decomposition reactions of mercuric arenesulphonate dihydrates
Publisher: CSIRO Publishing
Date: 1973
DOI: 10.1071/CH9730541
Abstract: Thermal decomposition of the mercuric arenesulphonate dihydrates Hg(03SR)2,- 2H20 (R = C6X5, p-HC6X4, or m-HC6C14 X = C1 or F) at c. 130-240" gave the corresponding diarylmercurials, the polyhalogenobenzenes RH, and sulphur trioxide (or sulphuric acid) in all cases, together with RS03H (R = C6F5 or p-HC6F4), and p-(p-HC6F4S03Hg),C6F4. By contrast, decomposition of Hg(03SR)2,2H20 (R = m-HC6F4 or o-HC6X4) gave the corresponding (-HgC6X4S03-), derivatives, sulphonic acids, polyhalogenobenzenes, and sulphur trioxide in all cases, together with m-HC6F4HgO3S-m-HC6F4 and o-(o-HC~C~~SOJH~),C~C~~. The compounds RHg03SR (R = C6C15, isolated as the monopyridinate, or p-HC6C14) were obtained from decomposition of the appropriate mercuric sulphonates at c. 165'. Identities of (-HgC6X4S03-), derivatives were established mainly by cleavage with triiodide ions in N,N-dimethylformamide giving the salts M(IC6X,S03) (M = Na or S-benzylthiouron- ium), and of (HC6X4S03Hg)2C6X4 derivatives by similar degradation giving 12C6X4 and M(HC6X4S03) (M = Na or Ph4As). Similar degradation of C6C15Hg03SC6C15,py, p-HC6Cl,Hg03S-p-HC6C14, and the known mercurials C6C15HgCl, (p-HC6C14),Hg, and (0-HC6C14),Hg gave the corresponding iodopolychlorobenzenes. The mercurated derivative (-o-H~C,F~SO~-)~ gave (-0-HgCsF4-)3 on thermal decomposition, and crystallization from water yielded ( - o - H ~ C ~ F ~ S ~ ~ - ) , , ~ ~ H ~ ~ , which was converted into (Ph4As)(o-C1HgC6F4S03) by tetraphenylarsonium chloride. The mercuric sulphonates were prepared from mercuric acetate and the appro- priate sulphonic acids in acetic acid (X = C1) or water (X = F). Sulphonic acids, obtained by sulphonation reactions, were characterized as the dihydrates and in some cases sodium salts (polychloro derivatives) or as barium and tetraphenylarsonium salts (tetrafluoro derivatives).
Organomercury compounds. XXV. The mercuration of 1,2,4-trichlorobenzene
Publisher: CSIRO Publishing
Date: 1981
DOI: 10.1071/CH9810301
Abstract: Mercuration of boiling 1,2,4-trichlorobenzene with mercuric trifluoroacetate yields complex species, which were shown to contain mainly �-(2,5,6-trichloro-1,3-phenylene)dimercury bridging units and 2,3,6-trichlorophenylmercury terminal groups by halogenodemercuration reactions, and bis(2,3,6-tri-chlorophenyl)mercury, which was independently synthesized from 2,3,6-trichlorophenyllithium and mercuric chloride. The organolithium compound was formed regiospecifically on reaction of 1,2,4-tri-chlorobenzene with butyllithium. Mercuration of 1,2,4-trichlorobenzene with mercuric trifluoroacetate (mole ratio 1 : 1) in trifluoroacetic acid results in regiospecific monomercuration giving 2,4,5-trichlorophenylmercuric trifluoroacetate. This compound undergoes rearrangement in boiling 1,2,4-trichlorobenzene to give a 2,3,6-trichlorophenylmercurial, and is considered to be an intermediate in the mercuration synthesis of bis(2,3,6-trichloropheny1)mercury. Thus, in 1,2,4-trichlorobenzene, the kinetically and thermodynamically favoured mercuration positions differ by contrast with the reported behaviour of 1,2,3-trichlorobenzene. Formation of the complex mercuration products is considered to involve �-(2,5,6-trichloro-1,3-phenylene)bis(trifluoroacetato)dimercury and bis(2,3,6-trichlorophenyl)mercury as intermediates. The new mercurials, bis(2,3,5-trichloro-phenyl)-, bis(3,4,5-trichlorophenyl)- and bis(2,4-dichlorophenyl)-mercury, have been prepared from the appropriate polychloroanilines by the diazonium route.
Lanthanoid‐Based Ionic Liquids Incorporating the Dicyanonitrosomethanide Anion
Publisher: Wiley
Date: 28-06-2012
Abstract: A series of low-melting-point salts with hexakisdicyanonitrosomethanidolanthanoidate anions has been synthesised and characterised: (C(2) mim)(3) [Ln(dcnm)(6)] (1 Ln 1 Ln=1 La, 1 Ce, 1 Pr, 1 Nd), (C(2) C(1) mim)(3) [Pr(dcnm)(6)] (2 Pr), (C(4) C(1) pyr)(3) [Ce(dcnm)(6)] (3 Ce), (N(1114))(3) [Ln(dcnm)(6)] (4 Ln 4 Ln=4 La, 4 Ce, 4 Pr, 4 Nd, 4 Sm, 4 Gd), and (N(1112OH) )(3) [Ce(dcnm)(6)] (5 Ce) (C(2) mim=1-ethyl-3-methylimidazolium, C(2) C(1) mim=1-ethyl-2,3-dimethylimidazolium, C(4) C(1) py=N-butyl-4-methylpyridinium, N(1114) =butyltrimethylammonium, N(1112OH) =2-(hydroxyethyl)trimethylammonium=choline). X-ray crystallography was used to determine the structures of complexes 1 La, 2 Pr, and 5 Ce, all of which contain [Ln(dcnm)(6)](3-) ions. Complexes 1 Ln and 2 Pr were all ionic liquids (ILs), with complex 3 Ce melting at 38.1 °C, the lowest melting point of any known complex containing the [Ln(dcnm)(6)](3-) trianion. The ammonium-based cations proved to be less suitable for forming ILs, with complexes 4 Sm and 4 Gd being the only salts with the N(1114) cation to have melting points below 100 °C. The choline-containing complex 5 Ce did not melt up to 160 °C, with the increase in melting point possibly being due to extensive hydrogen bonding, which could be inferred from the crystal structure of the complex.
The Interconversion of Tetrahalogenozincate(II) Complexes
Publisher: Informa UK Limited
Date: 1972
Steric engineering of C–F activation with lanthanoid formamidinates
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B419047E
Abstract: Reaction of lanthanum with Hg(C6F5)2 and bulky N,N'-bis(2,6-diisopropylphenyl)formamidine (HDippForm) in tetrahydrofuran gives [LaF{DippForm}2(THF)] with a rare terminal Ln-F bond, and a high yield of a novel functionalized formamidine, DippForm((CH2)4OC6F4H-o).
Alkali Metal/Lanthanoid Heterobimetallic Complexes of 8‐Hydroxyquinolines Accessed by Pseudo‐Solid‐State Reactions
Publisher: Wiley
Date: 18-08-2011
Symmetrization of Bromobis(polyfluorophenyl)thallium(III) compounds with copper powder
Publisher: CSIRO Publishing
Date: 1975
DOI: 10.1071/CH9751931
Abstract: Reaction of bromobis(polyfluorophenyl)thallium(III) compounds, R2TlBr (R = C6F5, p-HC6F4, m-HC6F4 or 3,5-H2C6F3) and (C6F5)2TlOH, with copper powder in boiling 1,4-dioxan (diox) or diethyl ether gave the corresponding tris(polyfluorophenyl)thallium(III) compounds, which were isolated as the complexes R3Tl,diox. By contrast, the derivatives R2TlBr (R = o- HC6F4, 3,6-H2C6F3 or Ph) failed to react, and (C6F5)2TlBr was decomposed by copper powder in boiling toluene yielding decafluorobiphenyl. Formation of tris(polyfluorophenyl)thallium(III) compounds is considered to occur via polyfluorophenylcopper(I) intermediates. Treatment of (C6F5)2TlBr with pentafluorophenylcopper in dioxan gave (C6F5)3Tl,diox. The new bromobis-(polyfluorophenyl)thallium(III) compounds, R2TIBr (R = p-HC6F4, m-HC6F4, o-HC6F4, 3,5-H2C6F3 or 3,6- H2C6F3), were prepared by reaction of thallic chloride with the appropriate Grignard reagents.
New lanthanoid biphenolate complexes, their further reactivity with trimethylaluminium and catalytic activity for the polymerisation of rac-lactide
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1DT02513A
Abstract: A series of rare earth biphenolate complexes of the general form [Ln(mbmp)(mbmpH)(thf) 3 ] have been synthesised by redox transmetallation rotolysis (RTP) and assessed for ROP activity of rac -lactide.
Reduction of Carbodiimides by Samarium(II) Bis(trimethylsilyl)amidesFormation of Oxalamidinates and Amidinates through C−C Coupling or C−H Activation
Publisher: American Chemical Society (ACS)
Date: 11-10-2007
DOI: 10.1021/IC701497C
Abstract: The reaction of [Sm{N(SiMe3)2}2(THF)2] (THF=tetrahydrofuran) with carbodiimides RN=C=NR (R=Cy, C6H3-2,6-iPr2) led to the formation of dinuclear SmIII complexes via differing C-C coupling processes. For R=Cy, the product [{(Me3Si)2N}2Sm(micro-C2N4Cy4)Sm{N(SiMe3)2}2] (1) has an oxalamidinate [C2N4Cy4]2- ligand resulting from coupling at the central C atoms of two CyNCNCy moieties. In contrast, for R=C6H3-2,6-iPr2, H transfer and an unusual coupling of two iPr methine C atoms resulted in a linked formamidinate complex, [{(Me3Si)2N}2Sm{micro-(RNC(H)N(Ar-Ar)NC(H)NR)}Sm{N(SiMe3)2}2] (2) (Ar-Ar=C6H3-2-iPr-6-C(CH3)2C(CH3)2-6'-C6H3-2'-iPr). Analogous reactions of RN=C=NR (R=Cy, C6H3-2,6-iPr2) with the SmII "ate" complex [Sm{N(SiMe2)3Na] gave 1 for R=Cy, but a novel C-substituted amidinate complex, [(THF)Na{N(R)C(NR)CH2Si(Me2)N(SiMe3)}Sm{N(SiMe3)2}2] (3), for R=C6H3-2,6-iPr2, via gamma C-H activation of a N(SiMe3)2 ligand.
Fullerene matrices in the MALDI-TOF mass spectroscopic characterisation of organometallic compounds
Publisher: Elsevier BV
Date: 02-2014
Novel Lanthanide-Based Polymeric Chains and Corresponding Ultrafast Dynamics in Solution
Publisher: American Chemical Society (ACS)
Date: 08-11-2011
DOI: 10.1021/IC201157M
Abstract: Two types of structurally related one-dimensional coordination polymers were prepared by reacting lanthanide trichloride hydrates [LnCl(3)·(H(2)O)(m)] with dibenzoylmethane (Ph(2)acacH) and a base. Using cesium carbonate (Cs(2)CO(3)) and praseodymium, neodymium, samarium, or dysprosium salts yielded [Cs{Ln(Ph(2)acac)(4)}](n) (Ln = Pr (1), Nd (2), Sm (3), Dy (4)) in considerable yields. Reaction of potassium tert-butoxide (KOtBu) and the neodymium salt [NdCl(3)·(H(2)O)(6)] with Ph(2)acacH resulted in [K{Nd(Ph(2)acac)(4)}](n) (5). All polymers exhibit a heterobimetallic backbone composed of alternating lanthanide and alkali metal atoms which are bridged by the Ph(2)acac ligands in a linear fashion. ESI-MS investigations on DMF solutions of 1-5 revealed a dissociation of all the five compounds upon dissolution, irrespective of the in idual lanthanide and alkali metal present. Temporal profiles of changes in optical density were acquired performing pump robe experiments with DMF solutions of 1-5 via femtosecond laser spectroscopy, highlighting a lanthanide-specific relaxation dynamic. The corresponding relaxation times ranging from seven picoseconds to a few hundred picoseconds are strongly dependent on the central lanthanide atom, indicating an intramolecular energy transfer from ligands to lanthanides. This interpretation also demands efficient intersystem crossing within one to two picoseconds from the S(1) to T(1) level of the ligands. Magnetic studies show that [Cs{Dy(Ph(2)acac)(4)}](n) (4) has slow relaxation of the magnetization arising from the single Dy(3+) ions and can be described as a single-ion single molecule magnet (SMM). Below 0.5 K, hysteresis loops of the magnetization are observed, which show weak single chain magnet (SCM) behavior.
Organoamido- and Aryloxo-Lanthanoids. XI. Syntheses and Crystal Structures of Nd(Odpp)3, Nd(Odpp)3(thf) and [Nd(Odpp)3(thf)2].2(thf) (Odpp-=2,6-Diphenylphenolate): Variations in Intramolecular π-Ph-Nd
Publisher: CSIRO Publishing
Date: 1995
DOI: 10.1071/CH9950741
Abstract: The X-ray crystal structure of Nd (Odpp)3 ( Odpp- = 2,6-diphenylphenolate), obtained by sublimation of Nd ( Odpp )3( thf )2 ( thf = tetrahydrofuran ) [triclinic, Pī , a 15.835(5), b 13.499(10), c 10.955(11) Ǻ, α 116.25(7), β 92.87(7), γ 101.66(6)°, V 2031 Ǻ3, Z2, No 5726 'observed' data (I 3σ(I)) refined to conventional R 0.047 shows a near triangular array of oxygens surrounding neodymium { Nd -O} 2.169 Ǻ, ∑ O- Nd -O 353.2° with additional, intramolecular Nd-η6-Ph chelate interactions { Nd -C} 3.046 Ǻ and Nd-η1-Ph ( Nd -C 2.964(7)Ǻ). There is a pseudotrigonal bipyramidal arrangement of the oxygens, the centroid of the η6-Ph, and the η1-carbon. The complex Nd ( Odpp )3( thf ), obtained by crystallization of Nd ( Odpp )3( thf )2 from toluene (monoclinic, P21/c, a 12.213(4), b 21.447(4), c 17.744Ǻ, β 104.25(2)°, V 4505 Ǻ3, Z 4, R 0.042 for No 8014) also has pseudotrigonal bipyramidal stereochemistry, with a triangular equatorial array of aryl oxide oxygens { Nd -O} 2.193 Ǻ ∑ O- Nd -O 358.7°, an apical thf oxygen (Nd -O 2.446(3)Ǻ), and an apical intramolecular chelating phenyl group. As the last has three Nd -C contacts (3.094(5), 3.144(5), 3.010(5)Ǻ) significantly shorter than the other three (3.300(5), 3.427(5), 3.377(5)Ǻ), an η3-Ph-Nd interaction seems likely. For [ Nd ( Odpp )3( thf )2].2( thf ), obtained by crystallization from tetrahydrofuran without drying of the crystals, the X-ray structure (monoclinic, P21, a 10.230(2), b 21.919(5), c 13.411(4) Ǻ, β 101.15(2)°, V 2950 A3, Z2, R 0.058 for No 3237) reveals a distorted trigonal bipyramidal arrangement of three aryl oxide oxygens (two equatorial 2.208(9), 2.16(1) Ǻ one axial 2.203(9) Ǻ) and two thf oxygens (one equatorial 2.44(1) Ǻ one axial (significantly distant) 2.62(1) Ǻ). The X-ray structure of [La( Odpp )3( thf )2].2( thf ) shows it to be isostructural with the neodymium analogue.
Organolanthanoids
Publisher: Elsevier BV
Date: 11-1979
Facile Oxidations of 1,4-Hydroquinones to 1,4-Benzoquinones with Bromomercury(II) Derivatives
Publisher: Informa UK Limited
Date: 1980
Preparations, infrared spectra, and structures of some zinc and cadmium arenesulphinates
Publisher: CSIRO Publishing
Date: 1971
DOI: 10.1071/CH9710935
Abstract: The complexes, M(O2SR)2,2H2O (M = Zn or Cd R = Ph or p-MeC6H4), have been prepared by metathesis reactions from the corresponding sodium arenesulphinates or arenesulphinic acids. Zinc benzenesulphinate has also been obtained from the reaction of diphenylzinc with sulphur dioxide and from the reduction of mercuric benzenesulphinate with zinc dust. Anhydrous zinc and cadmium arenesulphinates, M(O2SR)2, have been prepared by heating the dihydrates, and each cadmium complex has been obtained in two crystalline forms. From their isomorphism with the corresponding cobalt complexes, the zinc and cadmium arenesulphinate dihydrates have been shown to have octahedral stereochemistry. Both the hydrated and the anhydrous arenesulphinato complexes have sulphur- oxygen stretching frequencies indicative of O-sulphinate coordination, and polymeric structures based on bridging bidentate O-sulphinate groups are likely for all the complexes.
Pentabromophenylmercurials
Publisher: Elsevier BV
Date: 08-1975
Never a dull moment with praseodymium metal
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3DT00534H
Abstract: [BiI2(DippForm) 2 ], [BiII2(DippForm) 2 (C 6 F 5 ) 2 ] [Bi III (DippForm) 2 (C 6 F 5 )], [Pr(DippForm) 2 F(thf)]·PhMe, [ p -HC 6 F 4 DippForm]·0.5thf, and a ring-opened thf [ o -HC 6 F 4 O(CH 2 ) 4 DippForm] were obtained by the reaction of Pr metal with [Bi(C 6 F 5 ) 3 ]·0.5dioxane, DippFormH in thf.
Dependence of the Voltammetric Oxidation of the Photovoltaic Sensitizer : [(H[sub 3]-tctpy)Ru[sup II](NCS)[sub 3]][sup −] on the Electrode Material, Solvent, and Isomeric Purity
Publisher: The Electrochemical Society
Date: 2001
DOI: 10.1149/1.1342181
A Deca‐9‐Fluorenolato‐deca‐Samarium Oxide Cage
Publisher: Wiley
Date: 18-05-2018
Labile Pd-sulphur and Pt-sulphur bonds in organometallic palladium and platinum complexes [(COD)M(alkyl)(S-ligand)]n+—A speciation study
Publisher: Elsevier BV
Date: 12-2016
DOI: 10.1016/J.JINORGBIO.2016.06.009
Abstract: Reaction of various sulphur ligands L (SEt
The Infrared Spectra of Quaternary 'onium Cations of Group VB Elements. II. Vibrational Assignments for Some Tetraphenyl-, Triphenylmethyl-,Triphenylethyl-, Tetraethylphosphonium Salts
Publisher: CSIRO Publishing
Date: 1963
DOI: 10.1071/CH9630360
Abstract: The infrared spectra of five tetraphenylphosphonium salts, seven triphenylmethylphosphonium salts, five triphenylethylphosphonium salts, and three tetraethylphosphonium salts are reported, and tentative vibrational assignments are given for the majority of the observed bands.
Organomercury compounds
Publisher: Elsevier BV
Date: 05-1974
Organomercury Compounds. 32. Syntheses of Fluorophenylmercurials by Decarboxylation
Publisher: Wiley
Date: 06-1994
Syntheses of organorhodium(I) and organ oplatinum(II) compounds by decarboxylation
Publisher: Springer Science and Business Media LLC
Date: 12-1978
DOI: 10.1007/BF01393580
Steric Modulation of Coordination Number and Reactivity in the Synthesis of Lanthanoid(III) Formamidinates
Publisher: Wiley
Date: 25-09-2007
Abstract: Reactions of a range of the readily prepared and sterically tunable N,N'-bis(aryl)formamidines with lanthanoid metals and bis(pentafluorophenyl)mercury (Hg(C6F5)2) in THF have given an extensive series of tris(formamidinato)lanthanoid(III) complexes, [Ln(Form)3(thf)n], namely [La(o-TolForm)3(thf)2], [Er(o-TolForm)3(thf)], [La(XylForm)3(thf)], [Sm(XylForm)3], [Ln(MesForm)3] (Ln=La, Nd, Sm and Yb), [Ln(EtForm)3] (Ln=La, Nd, Sm, Ho and Yb), and [Ln(o-PhPhForm)3] (Ln=La, Nd, Sm and Er). [For an explanation of the N,N'-bis(aryl)formamidinate abbreviations used see Scheme 1.] Analogous attempts to prepare [Yb(o-TolForm)3] by this method invariably yielded [{Yb(o-TolForm)2(mu-OH)(thf)}2], but [Yb(o-TolForm)3] was isolated from a metathesis synthesis. X-ray crystal structures show exclusively N,N'-chelation of the Form ligands and a gradation in coordination number with Ln3+ size and with Form ligand bulk. The largest ligands, MesForm, EtForm and o-PhPhForm give solely homoleptic complexes, the first two being six-coordinate, the last having an eta1-pi-Ar--Ln interaction. Reaction of lanthanoid elements and Hg(C6F5)2 with the still bulkier DippFormH in THF resulted in C--F activation and formation of [Ln(DippForm)2F(thf)] (Ln=La, Ce, Nd, Sm and Tm) complexes, and o-HC6F4O(CH2)4DippForm in which the formamidine is functionalised by a ring-opened THF that has trapped tetrafluorobenzyne. Analogous reactions between Ln metals, Hg(o-HC6F4)2 and DippFormH yielded [Ln(DippForm)2F(thf)] (Ln=La, Sm and Nd) and 3,4,5-F3C6H2O(CH2)4DippForm. X-ray crystal structures of the heteroleptic fluorides show six-coordinate monomers with two chelating DippForm ligands and cisoid fluoride and THF ligands in a trigonal prismatic array. The organometallic species [Ln(DippForm)2(C[triple chemical bond]CPh)(thf)] (Ln=Nd or Sm) are obtained from reaction of Nd metal, bis(phenylethynyl)mercury (Hg(C[triple chemical bond]CPh)2) and DippFormH, and the oxidation of [Sm(DippForm)2(thf)2] with Hg(C[triple chemical bond]CPh)2, respectively. The monomeric, six-coordinate, cisoid [Ln(DippForm)2(C[triple chemical bond]CPh)(thf)] complexes have trigonal prismatic geometries and rare (for Ln) terminal C[triple chemical bond]CPh groups with contrasting Ln--C[triple chemical bond]C angles (Ln=Nd, 170.9(4) degrees Ln=Sm, 142.9(7) degrees). Their formation lends support to the view that [Ln(DippForm)2F(thf)] complexes arise from oxidative formation and C--F activation of [Ln(DippForm)2(C6F5)] intermediates.
The voltammetric reduction, deprotonation and surface activity of ruthenium photovoltaic sensitizers in acetone
Publisher: Elsevier BV
Date: 08-2001
Exploration of solvent free and/or microwave assisted syntheses of bismuth(iii) thiolates
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B708663F
Heterometallic CeIII???FeIII???salicylate networks: models for corrosion mitigation of steel surfaces by the ???Green??? inhibitor, Ce(salicylate)3
Publisher: Royal Society of Chemistry (RSC)
Date: 25-10-2002
DOI: 10.1039/B207722A
Abstract: The syntheses and structures of the novel Ce-Fe bimetallic complexes [[Fe(sal)2(bpy)]2Ce(NO3)(H2O)3].EtOH and [[Fe(sal)2(bpy)]4Ce2(H2O)11][salH]2.EtOH.3H2O (salH2 = salicylic acid) suggest Fe(3+)-sal2- units and Ce-OC(R)O-Fe bridging contribute to the formation of corrosion inhibitive layers on steel surfaces exposed to [Ce(salH)3(H2O)].
Organothallium compounds. XVIII. The effect of antimony pentafluoride and fluorosulfuric acid on the thallation of polyfluoroarenes
Publisher: CSIRO Publishing
Date: 1982
DOI: 10.1071/CH9821587
Abstract: The polyfluoroarenes m-H2C6F4, m-O2NC6F4H, m- and p-BrC6F4H, (p-HC6F4)2, C6F5H, 1,3,5-F3C6H3 and m-FSO2C6F4H have been thallated by thallic trifluoroacetate in fluorosulfuric acid in the presence of antimony pentafluoride. Substantial dithallation of m-H2F4 and 1,3,5-F3C6H3 and slight trithallation of the latter have been achieved. The products were identified by conversion into the corresponding polyfluoroiodoarenes on reaction with aqueous sodium iodide. From the reaction with pentafluorobenzene, pentafluorophenylthallium(III) species have been characterized. 1,2,4,5-Tetrafluoro-3-methoxybenzene was thallated by thallic trifluoroacetate in 1,2-dichloroethane in the presence of boron trifluoride etherate, but C6F5H and p-MeC6F4H failed to react.
A study of rare-earth 3-(4-methylbenzoyl)-propanoate compounds as corrosion inhibitors for AS1020 mild steel in NaCl solutions
Publisher: Elsevier BV
Date: 12-2018
The nature of sulphinate coordination in some organothallium sulphinates
Publisher: Elsevier BV
Date: 08-1970
Preparation of Mn(C6F5)2 compounds by treatment of Hg(C6F5)2 with manganese metal—a novel synthesis of d-block organometallics
Publisher: Elsevier BV
Date: 03-1993
Synthesis and Characterisation of Novel Bis(diphenylphosphane oxide)methanidoytterbium(III) Complexes
Publisher: MDPI AG
Date: 09-11-2022
DOI: 10.3390/MOLECULES27227704
Abstract: Reaction of [YbCp2(dme)] (Cp = cyclopentadienyl, dme = 1,2 dimethoxyethane) with bis(diphenylphosphano)methane dioxide (H2dppmO2) leads to deprotonation of the ligand H2dppmO2 and oxidation of ytterbium, forming an extremely air-sensitive product, [YbIII(HdppmO2)3] (1), a six-coordinate complex with three chelating (OPCHPO) HdppmO2 ligands. Complex 1 was also obtained by a redox transmetallation rotolysis synthesis from metallic ytterbium, Hg(C6F5)2, and H2dppmO2. In a further preparation, the reaction of [Yb(C6F5)2] with H2dppmO2, not only yielded compound 1, but also gave a remarkable tetranuclear cage, [Yb4(µ-HdppmO2)6(µ-F)6] (2) containing two [Yb(µ-F)]2 rhombic units linked by two fluoride ligands and the tetranuclear unit is encapsulated by six bridging HdppmO2 donors. The fluoride ligands of the cage result from C-F activation of pentafluorobenzene and concomitant formation of p-H2C6F4 and m-H2C6F4, the last being an unexpected product.
Complexation of a Novel Organoytterbium(II ) Ligand with Dimethylplatinum(II ): Crystal Structure of the Resulting Heterobimetallic Complex
Publisher: Wiley
Date: 10-1989
Bulky Ytterbium Formamidinates Stabilise Complexes with Radical Ligands, and Related Samarium “Tetracyclone” Chemistry
Publisher: Wiley
Date: 16-01-2017
Abstract: Divalent [Yb(DippForm)
A Half-Sandwich Perfluoroorganoytterbium(II) Complex from a Simple Redox Transmetalation/Ligand Exchange Synthesis
Publisher: American Chemical Society (ACS)
Date: 03-2003
DOI: 10.1021/OM021039A
Organomercury compounds. Vii. complexes of arylmercuric halides with bidentate ligands
Publisher: CSIRO Publishing
Date: 1968
DOI: 10.1071/CH9681757
Abstract: The complexes, C6F5HgXL2 [X = Br or C1 L2 = 2,2'-bipyridyl (bipy), 1,l0-phenanthroline (phen), 3,4,7,8-tetramethyl-1,l0-phenanthroline (tmp), or 2,9-dimethyl-1,l0-phenanthroline (dmp)], C6Cl5HgClL2 (L, = phen, tmp, or dmp), and PhHgClL2 (L2 = phen or tmp), have been prepared, but attempts to prepare PhHgCl bipy or complexes of phenylmercuric bromide were unsuccessful. Evidence that the complexes contain four coordinate mercury has been obtained from infrared spectroscopy. All complexes, except C6Cl5HgCl phen, C6Cl5HgCl dmp, and PhHgCl tmp, undergo complete or partial disproportionation reactions, 2RHgXL2 → L2HgX2 +R2HgL2 (or R2Hg + L2), in boiling benzene. Although disproportionation or low solubility precludes solution studies on the majority of the derivatives, it has been shown that C6F5HgX dmp complexes are monomeric in acetone and that PhHgCl phen undergoes dissociation, PhHgCl phen + PhHgCl + phen, in this solvent. Four-coordinate complexes of mercuric halides with neutral ligands, L,HgX, (L = a neutral unidentate or L, = a neutral bidentate ligand X = C1, Br, or I), are well kno~n,l-~ but analogous complexes of organomercuric halides, viz. RHgXL,, were unknown prior to this investigation. Reactions of organomercuric halides with ligands generally result in disproportionation, the corresponding diorganomercurial and mercuric halide complex being f~rmed.~-~ In some cases intermediate complexes RHgL+X- have been i~olated~,~ or detected in soluti~n,~-~~ and a 1 : 1 complex of unknown structure between pyridine and cis-2- * Part VI, J. organomet. Chem., in press. Preliminary communications for Part VII: Canty, A. J., Deacon, G. B., and Felder, P. W., Inorg. nzlcl. Chem. Lett., 1967,3,263 Deacon, G. B., and Canty, A. J., Inorg. %ucl. Chem. Lett., 1968, 4, 128. t Chemistry Department, Monash University, Clayton, Vie. 3168. Evans, R. C., Mann, F. G., Peiser, H. S., and Purdie, D., J. chem. Soc., 1940, 1209. Cass, R. C., Coates, G. E., and Hayter, R. G., J. chem. Soc., 1955, 4007. Coates, G. E., and Ridley, D., J. chem. Soc., 1964, 166. Coates, G. E. "Organometallic Compounds." 2nd. Edn, pp. 78-82. (Methuen: London 1960.) Seyferth, D., and Towe, R. H., Inorg. Chem., 1962, 1, 185. Coates, G. E., and Lauder, A., J. chem. Soc., 1965, 1857. Brodersen, K., Chem. Ber., 1957, 90, 2703. Schwarzenbach, G., and Schellenberg, & I., Helv. chim. Acta, 1965, 48, 28. Goggin, P. L., and Woodward, L. A., Trans. Faraday Soc., 1962, 58, 1495. Dessy, R. E., Budde, W. L., and Woodruff, C., J. Am. chem. Soc., 1962, 84, 1172. Aust. J. Chem., 1968, 21, 1757-67
Organolanthanides
Publisher: Elsevier BV
Date: 07-1977
Crystal structure of bis(benzo[h]quinolin-10-yl-C 10,N)dicarbonylruthenium(II)
Publisher: Royal Society of Chemistry (RSC)
Date: 1983
DOI: 10.1039/DT9830002121
Methanesulfonate and p-toluenesulfonate salts of the N-methyl-N-alkylpyrrolidinium and quaternary ammonium cations: novel low cost ionic liquids
Publisher: Royal Society of Chemistry (RSC)
Date: 17-04-2002
DOI: 10.1039/B201063A
The Use of Bismuth(III) Acetate in 'Wet' and 'Dry' Prevost Reactions
Publisher: CSIRO Publishing
Date: 1992
DOI: 10.1071/CH9921265
Abstract: cis -Diol and trans-diol derivatives can be prepared from alkenes by reaction with iodine and bismuth(III) acetate in 'wet' and 'dry' acetic acid, respectively. Reactions using lesser amounts of bismuth(III) acetate under 'dry' conditions give iodo acetates and under 'wet' conditions a mixture of iodohydrins and iodo ethers. Comparison of these reactions with those promoted by silver, copper, mercury and thallium salts is included.
Reactivity of [Sm(DippForm)2(thf)2] with substrates containing azo linkages
Publisher: Wiley
Date: 17-10-2023
New 'Green' Corrosion Inhibitors Based on Rare Earth Compounds
Publisher: CSIRO Publishing
Date: 2011
DOI: 10.1071/CH11092
Abstract: A series of rare earth organic compounds pioneered by our group have been shown to provide a viable alternative to the use of chromates as corrosion inhibitors for some steel and aluminium applications. For ex le we have shown that the lanthanum 4-hydroxy cinnamate offers excellent corrosion mitigation for mild steel in aqueous environments while rare earth diphenyl phosphates offer the best protection in the case of aluminium alloys. In both cases the protection appears to be related to the formation of a nanometre thick interphase occurring on the surface that reduces the electrochemical processes leading to metal loss or pitting. Very recent work has indicated that we may even be able to address the challenging issue of stress corrosion cracking of high strength steels. Furthermore, filiform corrosion can be suppressed when selected rare earth inhibitor compounds are added as pigments to a polymer coating. There is little doubt from the work thus far that a synergy exists between the rare earth and organic inhibitor components in these novel compounds. This paper reviews some of the published research conducted by the senior author and colleagues over the past 10 years in this developing field of green corrosion inhibitors.
The application of ATR-FTIR Spectroscopy and the Reversible DNA Conformation as a Sensor to Test the Effectiveness of Platinum(II) Anticancer Drugs
Publisher: MDPI AG
Date: 18-10-2018
DOI: 10.20944/PREPRINTS201810.0406.V1
Abstract: Platinum(II) complexes have been found to be effective against cancer cells. Cisplatin curbs cell replication by interacting with the deoxyribonucleic acid (DNA), eventually leading to cell death and reducing cell proliferation. In order to investigate the ability of platinum complexes to affect cancer cells, two ex les from the class of polyflurophenylorganoamidoplatinum(II) complexes were synthesised and tested on isolated DNA. The two compounds trans-[N,N& rsquo -bis(1,2,3,5,6-pentafluorophenyl)ethane-1,2-diaminato(1-)](2,3,4,5,6-pentafluorobenzoato)(pyridine)platinum(II) (PFB), and trans-[N,N& rsquo -bis(1,2,3,5,6-pentafluorophenyl)ethane-1,2-diaminato(1-)](2,4,6-trimethylbenzoato)(pyridine)platinum(II) (TMB) were compared with cisplatin through their reaction with DNA. Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy was applied to analyse the interaction of the Pt(II) complexes with DNA in the hydrated, dehydrated and rehydrated state. These were compared with control DNA in acetone/water (PFB, TMB) and isotonic saline (cisplatin) under the same conditions. Principle Component Analysis (PCA) was applied to compare the ATR-FTIR spectra of the untreated control DNA with spectra of PFB and TMB treated DNA s les. Disruptions in the conformation of DNA treated with the Pt(II) complexes upon rehydration were mainly observed by monitoring the position of the IR-band around 1711 cm-1 assigned to the DNA base-stacking vibration. Furthermore, other intensity changes in the phosphodiester bands of DNA at ~1234 cm-1 and 1225 cm-1 and shifts in the dianionic phosphodiester vibration at 966 cm-1 were observed. The isolated double stranded DNA (dsDNA) or single stranded DNA (ssDNA) showed different structural changes when incubated with the studied compounds. PCA confirmed PFB had the most dramatic effect by denaturing both dsDNA and ssDNA. Both compounds, along with cisplatin, induced changes in DNA bands at 1711, 1088, 1051 and 966 cm-1 indicative of DNA conformation changes. The ability to monitor conformational change with infrared spectroscopy paves the way for a sensor to screen for new anticancer therapeutic agents.
The synthesis of some alkyltelluride-manganese(I) complexes, and an assessment of their suitability for MOCVD applications
Publisher: Elsevier BV
Date: 04-1994
Successful extrapolation of an f-element synthetic method to the pseudo light lanthanoid, aluminium
Publisher: Elsevier BV
Date: 12-2010
Platinum complexes with the SC 6 F 4 H-4 ligand – Synthesis, structures and spectroscopy
Publisher: Elsevier BV
Date: 11-2014
Structural variations in rare earth benzoate complexes : Part II. Yttrium and terbium
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B708589C
Reactivity of Lanthanoid Aryloxide Complexes: Isolation of a 1,2‐Dimethoxyethane Cleavage Product
Publisher: Wiley
Date: 17-11-2008
The Infrared Spectra of Quaternary 'onium Cations of Group VB Elements. III. The X-Sensitive Vibration near 1100 cm-1
Publisher: CSIRO Publishing
Date: 1963
DOI: 10.1071/CH9630499
Synthesis and characterization of sodium, potassium, zinc and aluminium formamidinate complexes
Publisher: Informa UK Limited
Date: 02-2021
Molecular and Crystal Structures of Cp2YbX(THF) (X = Cl, Br)
Publisher: Wiley
Date: 07-2001
DOI: 10.1002/1521-3749(200107)627:7<1659::AID-ZAAC1659>3.0.CO;2-2
Metal based synthetic routes to heavy alkaline earth aryloxo complexes involving ligands of moderate steric bulk
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B903056E
Abstract: Treatment of an alkaline earth metal (Ca, Sr, Ba) with 2,4,6-trimethylphenol (HOmes) at elevated temperatures in the presence of mercury under solvent-free conditions, followed by extraction of the reaction mixture with 1,2-dimethoxyethane (dme), afforded dinuclear alkaline earth aryloxo complexes [Ae2(Omes)4(dme)4] (Ae = Ca 1, Sr 3, Ba 6). Extraction of the Ca metal and HOmes reaction mixture with thf afforded [Ca3(Omes)6(thf)] 2. In contrast, redox transmetallation ligand exchange reactions between an alkaline earth metal, diphenylmercury and HOmes in dme yielded solely 1 for Ca metal, a mixture of 3 and the methoxide bridged cage [Sr5(Omes)5(OMe)5(dme)4] x 2dme 4 for Sr metal, and solely [Ba5(Omes)5(OMe)5(dme)4] x dme 7 for Ba metal. The methoxide ligands originate from the C-O activation of the dme solvent. Treatment of liquid ammonia activated Sr or Ba metal with HOmes in thf afforded the linear species [Ae3(Omes)6(thf)6] (Ae = Sr 5, Ba 8), and 8 was also obtained from barium metal and HOmes in refluxing thf. The structures of 1 and 3, determined by X-ray crystallography, consist of two six coordinate Ae metal atoms, to each of which is bound a terminal aryloxide ligand, two bridging aryloxide ligands, and chelating and unidentate dme ligands. The structures of 4 and 7 contain five Ae metal atoms arranged on the vertices of a distorted square based pyramid. The Ae atoms are linked by four mu3-OMe ligands and a mu4-OMe ligand. Four bridging aryloxide ligands and four chelating dme ligands complete the coordination spheres of the four seven coordinate Ae atoms at the base of the pyramid, and a terminal aryloxide ligand is bound to the five coordinate apical Ae atom. The structures of 5 and 8 consist of a trinuclear linear array of Ae metal atoms, and contain solely bridging aryloxide ligands. Three thf ligands are bound to each terminal Ae atom, giving all Ae atoms a coordination number of six.
Transition Metal Thiocyanate Complexes of Picolylcyanoacetamides
Publisher: CSIRO Publishing
Date: 2017
DOI: 10.1071/CH16648
Abstract: A variety of transition metal complexes involving picolylcyanoacetamides (pica = NCCH2CONH-R R = 2-picolyl- (2pica), 3-picolyl- (3pica), 4-picolyl- (4pica)) and thiocyanate have been synthesised and their solid-state structures have been determined. The complexes were all obtained from reactions between the corresponding metals salts and pica ligands with sodium thiocyanate under ambient conditions. Both 3pica and 4pica coordinate to the metal solely through the nitrogen atom of the picolyl group and form discrete tetrahedral [M(NCS)2(pica)2] (3pica M = Mn, Zn 4pica M = Co) and octahedral [M(NCS)2(3pica)4] (M = Co, Fe, Ni) complexes. In addition, one-dimensional N,S-thiocyanate-bridged coordination polymers poly-[M(µ-NCS)2(pica)2] (3pica M = Cd 4pica M = Co, Cd) were obtained. The ligand 2pica gave the discrete octahedral complexes [Co(NCS)2(2pica)2] and [Cd(NO3)2(2pica)2] in which 2pica chelates in a bidentate fashion through its picolyl and carbonyl groups. Magnetic susceptibility measurements on the cobalt(ii) complexes were performed and showed short-range antiferromagnetic coupling for the [Co(NCS)2(4pica)2]n 1D polymer.
Assignments of metal–ligand vibrations for triphenylphosphine complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 1966
DOI: 10.1039/C19660000629
A simple one-pot route to stable formamidinatoiodidolanthanoid(iii ) complexes from lanthanoid metals
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1CC04080D
Abstract: Formamidinatoiodidolanthanoid( iii ) complexes [Ln(Form) n I 3− n ] (FormH = DFFormH or DippFormH) have been synthesized in good yields by one-pot direct reactions of the corresponding free metals with iodine and DFFormH or DippFormH in suitable ratios.
Role of Donor and Secondary Interactions in the Structures and Thermal Properties of Alkaline-Earth and Rare-Earth Metal Pyrazolates
Publisher: American Chemical Society (ACS)
Date: 09-11-2006
DOI: 10.1021/IC061294D
Abstract: The addition of neutral coligands to reduce the aggregation and improve the volatility of potential heavy alkaline-earth metal chemical vapor deposition (CVD) precursors has typically resulted in liberation of the coligand upon heating. A new series of dinuclear alkaline-earth and rare-earth metal pyrazolates, bis[bis(3,5-di-tert-butylpyrazolato)(tetrahydrofuran)calcium] (1), bis[bis(3,5-di-tert-butylpyrazolato)(tetrahydrofuran)strontium] (2), and bis[bis(3,5-di-tert-butylpyrazolato)bis(tetrahydrofuran)barium] (3), have been obtained from our previous donor-free oligonuclear complexes [{M(3,5-tBu2pz)2}n] (5, M = Ca, n = 3 6, M = Sr, n = 4 7, M = Ba, n = 6) by treatment with tetrahydrofuran (THF). Compounds 1-3, as well as the europium analogue bis[bis(3,5-di-tert-butylpyrazolato)(tetrahydrofuran)europium(II)] (4), can also be prepared by direct reaction of the metals and pyrazole in THF and anhydrous liquid ammonia. Recrystallization from hexane led to single crystals of 2-4, while the powder diffraction pattern of 1 revealed it to be isostructural with the previously published bis[bis(3,5-di-tert-butylpyrazolato)(tetrahydrofuran)ytterbium(II)] (8), providing important insight into differences and similarities between the two groups of metals. Detailed structural analysis of the compounds reveals secondary interactions including pi-bonding and agostic interactions, which are considered essential in stabilizing the metal complexes. The direct comparison of structural features and thermal properties (as evaluated by thermogravimetric analysis and sublimation studies) of the donor-free oligonuclear and the donor-containing dinuclear species offers a better understanding of the role of donors and secondary interactions.
Organolanthanoids. IV. Some reactions of Bis(polyfluorophenyl)ytterbium compounds
Publisher: CSIRO Publishing
Date: 1983
DOI: 10.1071/CH9830043
Abstract: From reactions of bis(polyfluorophenyl)ytterbium compounds R2Yb (R = C6Fs or p-HC6F4) with trans-Rh(CO)Cl(PPh3)2, NiCl2(bpy) (bpy = 2,2'-bipyridyl), NiCl2(PPh3)2, PtCl2(bpy)2 triphenyltin chloride, iodine and mercuric chloride, the polyfluorophenyl derivatives trans-RRh(CO)(PPh3)2, R2Ni(bpy), trans-(C6F5)2Ni(PPh3)2, (C6F5)2,Pt(bpy), Ph3SnC6Fs, C6F5I and (C6FS)2,Hg have been obtained. Reduction to mercury metal accompanied formation of the last compound. Carbonation of (C6F5)2Yb in tetrahydrofuran followed by acidification yields pentafluorobenzoic acid and, surprisingly, a significant amount of 2,3,4,5-tetrafluorobenzoic acid, in which the aromatic hydrogen is substantially derived from tetrahydrofuran. Reaction of (C6F5)2Yb with pentafluorobenzoic acid followed by acidification also gives 2,3,4,5-tetrafluorobenzoic acid. Fluoride elimination is less extensive and less specific in a similar reaction of YbI2.
Selective carbon-phosphorus bond cleavage: expanding the toolbox for accessing bulky divalent lanthanoid sandwich complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2CC00698G
Abstract: Tetra- and penta-phenyl cyclopentadienyldiphenylphosphine pro-ligands have been synthesised, which undergo selective C–P bond cleavage with lanthanoid metals (Ln = Eu, Sm and Yb), providing a new route to alent octa- and deca-phenylmetallocenes.
Thermal Degradation of Ionic Liquids at Elevated Temperatures
Publisher: CSIRO Publishing
Date: 2004
DOI: 10.1071/CH03221
Abstract: Ionic liquids based on the imidazolium cation are found to degrade, yielding volatile degradation products, at temperatures significantly lower than previously reported and thus a parameter Tz/x (the maximum operating temperature) is developed to provide a more appropriate estimate of thermal stability.
The synthesis of a new soluble samarium(II) diorganoamide
Publisher: Elsevier BV
Date: 12-1988
Tetradecanuclear polycarbonatolanthanoid clusters: Diverse coordination modes of carbonate providing access to novel core geometries
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT31101A
Abstract: The synthesis of two high nuclearity lanthanoid clusters demonstrates the versatility of the carbonate anion as a robust cluster forming agent, potentially allowing for the formation of otherwise inaccessible core topologies. The complexes, [Gd(14)(CO(3))(13)(ccnm)(9)(OH)(H(2)O)(6)(phen)(13)(NO(3))](CO(3))(2.5)·(phen)(0.5) (1) and [Dy(14)(CO(3))(13)(ccnm)(10)(OH)(H(2)O)(6)(phen)(13)](CO(3))(2.5)·(phen)(0.5) (2) (ccnm = carbamoylcyanonitrosomethanide, phen = 1,10-phenanthroline), contain a [Ln(14)(CO(3))(13)(OH)] core in which the carbonate anions display four unique coordination modes. The complexes are chiral, and the ccnm ligands also display four unique coordination modes. Extensive intra- and intermolecular π-π stacking between phen ligands leads to the formation of 1D chains in the crystal structure. Both complexes display magnetic properties that are indicative of antiferromagnetic coupling, with complex displaying behaviour consistent with possible single molecule magnet properties.
Antimony sources for MOCVD. The use of Et4Sb2 as a p-type dopant for Hg1−xCdxTe and crystal structure of the adduct [Et4Sb2 · 2CdI2]n
Publisher: Elsevier BV
Date: 05-1993
A simple synthesis of tetrahydrofuran complexes of lanthanoid trichlorides: convenient substitutes for anhydrous lanthanoid chlorides
Publisher: Royal Society of Chemistry (RSC)
Date: 1993
DOI: 10.1039/C39930001328
Complexes of four-membered group 13 metal(I) N-heterocyclic carbene analogues with platinum(II) fragments
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B821984B
Abstract: A series of fluorinated bis(aryl)platinum(II) complexes, cis-[Pt(Ar(f))2(1,5-C6H10)] (Ar(f) = p-C6HF4, p-C6(OMe)F4 or C6H2F(3-)2,4,6) were reacted with the four-membered gallium(I) or indium(I) heterocycles, [:E{[N(Ar)]2CN(C6H11)2}] (E = Ga or In, Ar = C6H3Pr(i)(2-)2,6) under various stoichiometries. These yielded either the 2:1 complexes, cis-[Pt(Ar(f))2{Ga{[N(Ar)]2CN(C6H11)2}}2], trans-[Pt(C6H2F(3-)2,4,6)2{Ga{[N(Ar)]2CN(C6H11)2}}2] and trans-[Pt(Ar(f))2{In{[N(Ar)]2CN(C6H11)2}}2], or the 3:1 complexes, trans-[Pt(Ar(f))2{In{[N(Ar)]2CN(C6H11)2}}3] (Ar(f) = p-C6HF4 or p-C6(OMe)F4), all of which were crystallographically characterised. The differing outcomes of these reactions are explained in terms of the lesser nucleophilicity and greater electrophilicity of the indium heterocycle relative to its gallium counterpart. In the solid state, and in solution, the 3:1 indium complexes exhibit strong intramolecular In...F interactions which are indicative of their heterocyclic ligands displaying rare ex les of "Lewis hoteric" behaviour. An unusual platinum(0) complex in which the indium(I) heterocycle acts as a mu3-bridging ligand, [{Pt(norbornene)}3{mu3-In{[N(Ar)]2CN(C6H11)2}}2], was also prepared and structurally authenticated.
Errata corrige
Publisher: Springer Science and Business Media LLC
Date: 12-1982
DOI: 10.1007/BF00618355
Synthesis of divalent aryloxy- and diorganoamido-lanthanides from bis(pentafluorophenyl)lanthanide(II) complexes
Publisher: Elsevier BV
Date: 1987
Monomeric Tris(η2‐pyrazolato)Lanthanoid Complexes with the Bulky 3,5‐Di(tert‐butyl)pyrazolato Ligand
Publisher: Wiley
Date: 06-1993
Organolanthanoids. XIII. Bis(pentadeuterocyclopentadienyl)ytterbium(II)
Publisher: Elsevier BV
Date: 02-1988
Bis(pentafluorophenyl)mercury—a versatile synthon in organo-, organooxo-, and organoamido-lanthanoid chemistry
Publisher: Elsevier BV
Date: 03-2002
p-Type doping of Hg0.4Cd0.6Te using Et4Sb2
Publisher: Elsevier BV
Date: 05-1994
A supramolecular twist to the structures of bis(polyfluorophenyl)mercurials
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0CE00258E
Unexpected Formation of Bis(1H‐7‐azaindol‐3‐yl)(2,4,5‐trimethylphenyl)methane by Erbium Metal‐Induced CH Activation
Publisher: Wiley
Date: 09-2003
Abstract: Reaction of 7‐azaindole (azinH) and 1,2,4,5‐tetramethylbenzene (durene) in the presence of erbium metal and mercury at 170 °C under vacuum induced an unusual CC bond formation between a methyl group of durene and C3 of two azinH molecules yielding bis(1 H ‐7‐azaindol‐3‐yl)(2,4,5‐trimethylphenyl)methane { 2: IUPAC name 3‐[1 H ‐pyrrolo[2,3‐ b ]pyridin‐3‐yl(2,4,5‐trimethylphenyl)methyl]‐1 H ‐pyrrolo[2,3‐ b ]pyridine}. The structure of 2 was established by X‐ray crystallography and supported by IR, NMR and mass spectroscopy.
Synthesis and Structures of Rare Earth 3-(4′-Methylbenzoyl)-propanoate Complexes-New Corrosion Inhibitors
Publisher: CSIRO Publishing
Date: 2017
DOI: 10.1071/CH16547
Abstract: A series of rare earth 3-(4′-methylbenzoyl)propanoate (mbp–) complexes [RE(mbp)3(H2O)] (RE = rare earth = Y, La, Ce, Nd, Ho, Er) have been prepared by either metathesis reactions between the corresponding rare earth chloride and Na(mbp) or protolysis of rare earth acetates by the free acid. Single-crystal X-ray diffraction studies of [RE(mbp)3(H2O)] (RE = Ce, Nd) and [Ce(mbp)3(dmso)] reveal a 1D carboxylate-bridged polymeric structure in the solid state, featuring 9-coordinate rare earth ions. X-ray powder diffraction patterns of the bulk materials indicates that all of the [RE(mbp)3(H2O)] complexes except RE = La are isomorphous. Hence, there is no structural change from the complex with RE = Ce to that with RE = Er despite the lanthanoid contraction. The 1H NMR spectra of the RE = Ho or Er complexes in (CD3)2SO show large paramagnetic shifts and broadening of the CH2 resonances, indicating the retention of substantial carboxylate coordination in solution.
Lanthanoid and Alkaline Earth Complexes Involving New Substituted Pyrazolates
Publisher: CSIRO Publishing
Date: 2012
DOI: 10.1071/CH12069
Abstract: From the pyrazoles 3,5-di-(2′-furanyl)pyrazole (fu2pzH), 3-phenyl-5-(2′-thienyl)pyrazole (PhtpzH) and 3-(2′-furanyl)-5-(2′′-naphthyl)pyrazole (funappzH), a range of alkaline earth and lanthanoid pyrazolate complexes has been prepared by redox transmetallation rotolysis reactions between free metals, Hg(C6F5)2 and the pyrazoles, by reaction of I2‐activated metals with the pyrazoles, and in one case by a similar reaction of unactivated metal, in the donor solvents tetrahydrofuran (thf) and 1,2-dimethoxyethane (dme). Thus the alent [Ca(Phtpz)2(thf)4], [Ba(Phtpz)2(thf)4] and [Ca(funappz)2(thf)4]·(thf) complexes, the heteroleptic [Yb(Phtpz)I(thf)4] and the trivalent [La(fu2pz)3(thf)3]·2thf complex have been prepared and structurally characterized, as well as the dme complexes [Yb(Phtpz)2(dme)2] and [Eu(Phtpz)3(dme)2]. Highlights include the first trans-[LnII(pz)I(thf)4] complex, a rare transoid [Ln(pz)2(dme)2] complex and a complex with both chelating and unidentate dme. In all cases, the Phtpz complexes exhibit pronounced positional disorder of the 2-thienyl and phenyl groups in the solid state, as do the two polymorphs of the parent pyrazole.
Formation of HoIII Trinuclear Clusters and GdIII Monodimensional Polymers Induced by ortho and para Regioisomers of Pyridyl‐Functionalised β‐Diketones: Synthesis, S
Publisher: Wiley
Date: 02-2009
Organolanthanoids XVIII. The synthesis and X-ray crystal structure of di[η-chlorobis(diphenylphosphino-η5-cyclopentadienyl)ytterbium(III)]
Publisher: Elsevier BV
Date: 12-1993
Novel organomercury complexes
Publisher: Elsevier BV
Date: 07-1967
Syntheses of polyfluorophenylcobalt(III) schiff base complexes using organothallium reagents
Publisher: Elsevier BV
Date: 1976
Di(phenylmercuri)ammonium compounds
Publisher: Royal Society of Chemistry (RSC)
Date: 1968
DOI: 10.1039/J19680001182
Divalent ansa-Octaphenyllanthanocenes: Synthesis, Structures, and EuII Luminescence
Publisher: American Chemical Society (ACS)
Date: 13-06-2023
A simple synthesis and a structural survey of homoleptic rare earth(III) 2,6-diphenylphenolates
Publisher: Royal Society of Chemistry (RSC)
Date: 2000
DOI: 10.1039/A910277I
Lanthanoid Biphenolates as a Rich Source of Lanthanoid‐Main Group Heterobimetallic Complexes
Publisher: Wiley
Date: 27-01-2022
Abstract: Several new trivalent dinuclear rare earth 2,2’‐methylenebis(6‐ tert ‐butyl‐4‐methylphenolate) (mbmp 2− ) complexes with the general form [Ln 2 (mbmp) 3 (thf) n ] (Ln=Sm 1, Tb 2 (n=3), and Ho 3, Yb 4 (n=2), and a tetravalent cerium complex [Ce(mbmp) 2 (thf) 2 ] (5) have been synthesised by RTP (redox transmetallation rotolysis) reactions from lanthanoid metals, Hg(C 6 F 5 ) 2 and the biphenol mbmpH 2 . These new complexes and some previously reported partially protonated rare earth biphenolate complexes [Ln(mbmp)(mbmpH)(thf) n ] react with lithium, aluminium, potassium and zinc organometallic reagents to form lanthanoid‐main group heterobimetallic species. When reaction mixtures containing the Ln biphenolate complexes were treated with n ‐butyllithium, both molecular ([Li(thf) 2 Ln(mbmp) 2 (thf) n ] (Ln=La 6, Pr 7 (n=2) and Er 8, Yb 9, and Lu 10 (n=1)) and charge separated ([Li(thf) 4 ][Ln(mbmp) 2 (thf) 2 ] (Ln=Y 11, Sm 12, Dy 13, and Ho 14) complexes were isolated. Treatment with trimethylaluminium also led to isolation of molecular ([AlMe 2 Ln(mbmp) 2 (thf) 2 ] (Ln=Pr 15, Sm 16, and Tb 17)) and ionic [La(mbmp)(thf) 5 ][AlMe 2 (mbmp)] (18) complexes. One gadolinium‐potassium ([K(thf) 3 Gd(mbmp) 2 (thf) 2 ] (19)), and one ytterbium‐zinc species ([ZnEtYb(mbmp) 2 (thf)] (20)) were isolated from treatment of reaction mixtures with potassium bis(trimethylsilyl)amide and diethylzinc respectively.
Syntheses, Structures, and Corrosion Inhibition of Various Alkali Metal Carboxylate Complexes
Publisher: MDPI AG
Date: 19-07-2023
DOI: 10.3390/MOLECULES28145515
Abstract: Complexes of the alkali metals Li-Cs with 3-thiophenecarboxylate (3tpc), 2-methyl-3-furoate (2m3fur), 3-furoate (3fur), 4-hydroxycinnamate (4hocin), and 4-hydroxybenzoate (4hob) ions were prepared via neutralisation reactions, and the structures of [Li2(3tpc)2]n (1Li) [K2(3tpc)2]n (1K) [Rb(3tpc)(H2O)]n (1Rb) [Cs{H(3tpc)2}]n (1Cs) [Li2(2m3fur)2(H2O)3] (2Li) [K2(2m3fur)2(H2O)]n (2K) [Li(3fur)]n(3Li) [K(4hocin](H2O)3]n (4K) [Rb{H(4hocin)2}]n.nH2O (4Rb) [Cs(4hocin)(H2O)]n (4Cs) [Li(4hob)]n (5Li) [K(4hob)(H2O)3]n (5K) [Rb(4hob)(H2O)]n (5Rb) and [Cs(4hob)(H2O)]n (5Cs) were determined via X-ray crystallography. Bulk products were also characterised via XPD, IR, and TGA measurements. No sodium derivatives could be obtained as crystallographically suitable single crystals. All were obtained as coordination polymers with a wide variety of carboxylate-binding modes, except for dinuclear 2Li. Under conditions that normally gave coordinated carboxylate ions, the ligation of hydrogen dicarboxylate ions was observed in 1Cs and 4Rb, with short H-bonds and short O…O distances associated with the acidic hydrogen. The alkali-metal carboxylates showed corrosion inhibitor properties inferior to those of the corresponding rare-earth carboxylates.
Contrasting Binding Modes in Lanthanoid Pyrazolate and Pseudo-pyrazolates Prepared by Oxidation of Lanthanoid(II) Complexes and Lanthanoid Metals with Thallium(I) Reagents
Publisher: American Chemical Society (ACS)
Date: 30-03-2000
DOI: 10.1021/OM990932F
A Polyfunctional Lewis Acid with Antifacial µ3-N,N-Dimethylformamide Ligands in [(o-HgC6F4)3(dmf)2]
Publisher: CSIRO Publishing
Date: 2002
DOI: 10.1071/CH02039
Abstract: In [(o-HgC6F4)3(dmf)2], the cyclotrimeric tetrafluoro-o-phenylenemercury(II) molecule is ligated by two m3-dmf-O molecules above (Hg-O 2.837(7), 2.895(5), 3.036(5) �) and below (Hg-O 2.820(5), 2.863(6), 2.927(6) �) the Hg3 plane with the two oxygens and the three mercury atoms in a trigonal bipyramidal arrangement about the centroid of the Hg3 plane.
HSAB theory applied to rearrangements in the mass spectra of organometallic compounds
Publisher: Elsevier BV
Date: 1979
Organomercury compounds. IX. Preparations, structures, and thermal decomposition of arylmercuric arenesulphinates
Publisher: CSIRO Publishing
Date: 1969
DOI: 10.1071/CH9690549
Abstract: The arylmercuric arenesulphinates, PhHg(SO2Ph), p-MeC6H4Hg(SO2-p-MeC6H4), PhHg(SO2-p-MeC6H4), p-MeC6H4Hg(SO2Ph), and C6F5Hg(SO2Ph), have been prepared by reaction of mercuric benzenesulphinate or p- toluenesulphinate with the appropriate diarylmercury compound in chloroform or methanol, and the first three compounds have also been obtained by reaction of liquid sulphur dioxide with diphenylmercury, di-p-tolylmercury, or phenyl-p-tolylmercury. Linkage isomers of phenylmercuric benzenesulphinate have been prepared. Isomer A, obtained from chloroform-pentane, is considered to be a monomeric O-sulphinato complex, and isomer B, obtained from cold acetone, methyl ethyI ketone, or methanol, to be an S-sulphinato complex. The isomers are readily interconverted. In chloroform, deuterochloroform, and acetone, at room temperature, only the O-sulphinato complex can be detected. The other arylmercuric arenesulphinates have the same structure as isomer A. Linkage isomers could not be isolated for these derivatives. However, there is evidence that p-MeC6H4Hg(SO2Ph) slowly isomerizes in the solid state to give the corresponding S-sulphinato complex. Thermal decomposition of PhHg-(SO2Ph) (both isomers), p-MeC6H4Hg(SO2-p-MeC6H4), PhHg(SO2-p-MeC6H4), and p-MeC8H4Hg(SO2Ph) gives sulphur dioxide and the corresponding diarylmercurycompound.
GIVING PROPRANOLOL TABLETS TO INFANTS WITH HEMANGIOMAS – SOLUBILITY IN WATER
Publisher: Wiley
Date: 07-2011
Syntheses of organoytterbium(III) compounds by oxidation of dicyclopentadienylytterbium(II). Crystal structure of [η-C5H5)2Yb(O2CC6F5)]2
Publisher: Elsevier BV
Date: 12-1984
Linear Finite “Mers”—Homoleptic Polynuclear Heavy Alkaline Earth Metal Pyrazolates
Publisher: Wiley
Date: 29-09-2004
Homo- and Heteroleptic 8-Quinaldinolate Complexes From Elevated-temperature Rearrangements
Publisher: CSIRO Publishing
Date: 2013
DOI: 10.1071/CH13185
Abstract: Three new zinc 8-quinaldinolate complexes have been obtained from rearrangement reactions at elevated temperatures including the first homoleptic zinc 8-quinaldinolate complex. The homoleptic, trinuclear complex [Zn3(MQ)6] (1) (MQ = 8-quinaldinolate) was obtained by the recrystallisation of amorphous Zn(MQ)2 from a 1,2,4,5-tetramethylbenzene flux at 270°C. The heteroleptic complexes [Zn4Cl4(MQ)4] (2) and [Zn4Cl2(MQ)6] (3) were simultaneously obtained by the reaction between Zn(MQ)2 and anhydrous ZnCl2 under the same conditions. All complexes contain quinaldinolate ligands in a mixed chelating–bridging coordination mode. The homoleptic complex adopts a V-shaped geometry whereas the heteroleptic complexes adopt closely related cyclic structures.
Carbon bridged biphenolate ligands in rare earth chemistry
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2NJ04358K
Abstract: This review highlights rare earth biphenolates as they offer a ersity over simpler aryloxides, as well as their efficacy as catalysts and initiators in organic transformations and polymerisations.
A sulphur dioxide adduct of triphenylindium
Publisher: Elsevier BV
Date: 04-1974
Synthetic and structural comparisons of bismuth(iii) carboxylates synthesised under solvent-free and reflux conditions
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B605002F
Abstract: Two synthetic approaches to the formation of bismuth(III) carboxylates have been explored and compared. Ph(3)Bi was reacted with a series of carboxylic acids (RCO(2)H) of varying pK(a) and functionality (R = PhCH[double bond, length as m-dash]CH, o-MeOC(6)H(4), m-MeOC(6)H(4), o-H(2)NC(6)H, o-O(2)NC(6)H(4), p-O(2)NC(6)H(4), 2-(C(5)H(4)N)) under reflux conditions in toluene and solvent-free. The thermochemical profiles of the solvent-free reactions were also studied by DSC-TGA. All reactions produced the tri-substituted bismuth carboxylates in comparable yields and purity with the exceptions of picolinic acid and p-nitrobenzoic acid. 2-Picolinic acid exclusively formed the di-substituted complex, [PhBi(2-(C(5)H(4)N)CO(2))(2)](4), by both methods, while p-nitrobenzoic acid gave the tri-substituted complex through reflux and the di-substituted complex under solvent-free conditions. Two of the complexes were structurally authenticated by single crystal X-ray diffraction: [PhBi(2-(C(5)H(4)N)CO(2))(2)](4) is tetrameric formed through five membered chelate rings involving the pyridyl N and O(-C) rather than the less stable carboxylate (-CO(2)) chelates, while [Bi(o-MeOC(6)H(4)CO(2))(3)](infinity), is a polymer in which dimeric units, constructed around two chelating and one unsymmetrical bridging carboxylate on each Bi centre, are then joined together through longer intermolecular Bi-O bridging bonds.
New homoleptic anionic aryloxolanthanide(III) complexes with unusual coordination trapping of the alkali-metal counter ions
Publisher: Royal Society of Chemistry (RSC)
Date: 1996
DOI: 10.1039/CC9960001729
Reactions of lanthanide elements with thallous cyclopentadienide—A new route to cyclopentadienyllanthanides
Publisher: Elsevier BV
Date: 1982
Trivalent Rare Earth Complexes of the Unsymmetrical 3‐(2′‐Thienyl)‐5‐(trifluoromethyl)pyrazolate Ligand
Publisher: Wiley
Date: 19-07-2011
Synthesis and Characterisation of Rare Earth Complexes Supported by para‐Substituted Cinnamate Ligands
Publisher: Wiley
Date: 05-2009
Abstract: The preparations and characterisations of a range of lanthanoid 4‐( R )‐substituted (4‐Rcinn, R = OH, OMe, NO 2 , Cl), known to have good anticorrosion properties, are reported. The crystal structure of [Ce(4‐OHcinn) 3 (MeOH) 2 (H 2 O)]·MeOH is a polymer, in which the cerium atoms are nonacoordinate, and adjacent cerium atoms are bridged by either two bridging bidentate or two bridging tridentate carboxylate ligands. Each cerium atom also has one monodentate 4‐hydroxycinnamate ligand, one aqua ligand, and two methanol ligands.
The Solvent Properties of Trifluoroiodomethane
Publisher: CSIRO Publishing
Date: 1963
DOI: 10.1071/CH9631132
Synthesis of Heteroleptic Bis(diimine)carbonylchlororuthenium(II) Complexes from Photodecarbonylated Precursors
Publisher: American Chemical Society (ACS)
Date: 02-04-2004
DOI: 10.1021/IC0351895
Abstract: The reactions of bidentate diimine ligands (L2) with binuclear [Ru(L1)(CO)Cl2]2 complexes [L1 not equal to L2 = 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (4,4'-Me2bpy), 5,5'-dimethyl-2,2'-bipyridine (5,5'-Me2bpy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), 5,6-dimethyl-1,10-phenanthroline (5,6-Me2phen), di(2-pyridyl)ketone (dpk), di(2-pyridyl)amine (dpa)] result in cleavage of the dichloride bridge and the formation of cationic [Ru(L1)(L2)(CO)Cl]+ complexes. In addition to spectroscopic characterization, the structures of the [Ru(bpy)(phen)(CO)Cl]+, [Ru(4,4'-Me2bpy)(5,6-Me2phen)(CO)Cl]+ (as two polymorphs), [Ru(4,4'-Me2bpy)(4,7-Me2phen)(CO)Cl]+, [Ru(bpy)(dpa)(CO)Cl]+, [Ru(5,5'-Me2bpy)(dpa)(CO)Cl]+, [Ru(bpy)(dpk)(CO)Cl]+, and [Ru(4,4'-Me2bpy)(dpk)(CO)Cl]+ cations were confirmed by single crystal X-ray diffraction studies. In each case, the structurally characterized complex had the carbonyl ligand trans to a nitrogen from the incoming diimine ligand, these complexes corresponding to the main isomers isolated from the reaction mixtures. The synthesis of [Ru(4,4'-Me2bpy)(5,6-Me2bpy)(CO)(NO3)]+ from [Ru(4,4'-Me2bpy)(5,6-Me2bpy)(CO)Cl]+ and AgNO3 demonstrates that exchange of the chloro ligand can be achieved.
Rare-earth N,N′-diarylformamidinate complexes
Publisher: Elsevier BV
Date: 06-2017
Organolanthanoids. XV. The Preparation of Carboxylatobis(cyclopentadienyl)ytterbium(III) Complexes by Oxidation of Bis(cyclopentadienyl)ytterbium(II)
Publisher: CSIRO Publishing
Date: 1989
DOI: 10.1071/CH9890845
Abstract: The complexes, Cp2Yb(O2CR) [Cp = cyclopentadienyl R = Me, CF3, Ph, C6F5, C6Br5, o- MeO2CC6F4 (tmcp), 2,4,6-Me3C6H2 (tmp), pyridin-2-yl (pyr), or quinolin-2-yl (quin)] have been prepared in good yield by oxidation of bis(cyclopentadienyl)(1,2-dimethoxyethane)ytterbium(II) with the appropriate mercury(ll) or thallium(I) carboxylate, generally in tetrahydrofuran. Structural data suggest that four complexes (R=Me, CF3, Ph or C6F5) are dimeric with bridging bidentate carboxylate groups, three (R = tmp, pyr or quin) are monomeric with chelating carboxylates, but the structure is less clear for R = C6Br5 or tmcp. Unit cell dimensions have been determined for bis(cyclopentadienyl)(2,4,6-trimethyibenzoato)ytterbium(III), but the structure could not be solved owing to decomposition of single crystals in the X-ray beam.
Organomercury compounds
Publisher: Elsevier BV
Date: 08-1973
Direct Reaction – One Step Route to Synthesize Lanthanoid‐iodide Formamidinates**
Publisher: Wiley
Date: 26-05-2023
Abstract: This paper describes a novel and simple method – direct reaction of lanthanoid metals with equimolar amounts of iodine and a formamidine under ultrasonication as an effective, metal‐based route to lanthanoid(III) diiodide formamidinates, namely I . N,N ′‐Bis(2,6‐diisopropylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(DippForm)I 2 (thf) 3 ] (Ln=La, 1 , Ce, 2 , Tb, 3 , Ho, 4 , Er, 5 , Tm, 6 ) II . N,N ′‐Bis(2,6‐diethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(EtForm)I 2 (thf) 3 ] (Ln=Ce, 7 , Nd, 8 , Gd, 9 , Tb, 10 , Dy, 11 , Ho, 12 , Er, 13 , Lu, 14 ). III . N,N ′‐bis(2,6‐dimethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(XylForm)I 2 (thf) 3 ] (Ln=Ce, 15 , Nd, 16 , Gd, 17 , Tm, 18 , Lu 19 ) IV . N,N ′‐bis(phenyl)formamidinatodiiodidolanthanoid complexes [Ln(PhForm)I 2 (thf) 3 ] (Ln=Nd, 20 , Gd, 21 , Er, 22 ). Compound [Ce(XylForm) 2 I(thf) 2 ] ( 23 ) was also synthesized by the same method except the ratio of I 2 to XylFormH was 1 : 4. Divalent N,N ′‐bis(2,6‐diisopropylphenyl)formamidinato‐iodido‐lanthanoid(II) complexes [Eu(DippForm)I(thf) 4 ] ⋅ thf ( 24 ), [Yb(DippForm)I(thf) 3 ] ⋅ 2DippFormH ( 25 ), [Sm(DippForm)I(thf) 4 ] ⋅ thf ( 26 ) have also been synthesized by direct reactions of the free metals, iodine and DippFormH. Interestingly, [Sm(DippForm)I 2 (thf) 3 ] ( 27 ) was obtained by the oxidation of [Sm(DippForm)I(thf) 4 ] ⋅ thf ( 26 ) on exposure to air. N,N ′‐Bis(2,6‐dimethylphenyl)formamidinatoiodidosamarium(II) [Sm(XylForm)I(thf) 3 ] n ( 28 ) was also prepared by direct reaction of Sm, iodine and XylFormH (mole ratio of I 2 : XylFormH=1 : 2). All products have been identified by X‐ray crystallography and all the trivalent complexes [Ln(Form) n I 3‐n ] (n=1 or 2) are stable to rearrangement.
Density functional theory and surface enhanced Raman spectroscopy characterization of novel platinum drugs
Publisher: Wiley
Date: 2002
DOI: 10.1002/BIP.10091
Abstract: There is considerable interest in the development of novel platinum‐based anticancer drugs that overcome the disadvantages associated with the widely used drug cisplatin, which are its inactivity against some types of tumors and its toxic side effects. In this study we show the suitability of normal Raman spectroscopy (NRS) and surface enhanced Raman spectroscopy (SERS), assisted by density functional theoretical (DFT) calculations, for the characterization of Pt complexes. The Pt complexes studied include the established drugs cisplatin and carboplatin, as well as five novel Pt complexes with anticancer activity. DFT calculations at the B3LYP/LanL2DZ level are a good prediction of the experimental NRS spectra of small and medium sized Pt complexes. The use of SERS allows the investigation of Pt complexes at physiological concentrations, and the binding strengths of the different ligands can be determined. The formation of positively charged hydrolysis products may be necessary for SERS activity. The exiting group in the hydrolysis reaction can be identified. © 2002 Wiley Periodicals, Inc. Biopolymers (Biospectroscopy) 67: 294–297, 2002
Supramolecular Architecture and a New Mode of Pyrazolate Coordination (η3) in the First Homoleptic Lanthanide Pyrazolate Complexes
Publisher: Wiley
Date: 14-06-1999
DOI: 10.1002/(SICI)1521-3773(19990614)38:12<1766::AID-ANIE1766>3.0.CO;2-I
Synthesis and structures of calcium and strontium 2,4-di-tert-butylphenolates and their reactivity towards the amine co-initiated ring-opening polymerisation of rac-lactide
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3DT00065F
Abstract: Calcium and strontium metals react with Hg(C6F5)2 and 2,4-di-tert-butylphenol (H-DBP) in tetrahydrofuran (THF) and 1,2-dimethoxyethane (DME) to give [Ca(DBP)2(THF)4] (1), [Ca2(DBP)4(DME)4(μ-DME)] (2), [Sr3(μ-DBP)6(THF)6] (3), and [Sr2(DBP)(μ-DBP)3(DME)3] (4). Compound 1 is a six coordinate trans-octahedral monomer, whereas in binuclear 2 two seven-coordinate Ca centres are bridged by a DME ligand. In 3 a central Sr is connected by three bridging DBP groups to each of two terminal Sr(THF)3 moieties, all metal atoms being six coordinate. Compound 4 has one six- and one seven-coordinate Sr, bridged by three DBP ligands, the former Sr also having a terminal DBP and a bidentate DME ligand and the latter two DME ligands. Complexes 2 and 4 act as ring-opening polymerisation (ROP) catalysts for the benzyl alcohol or benzylamine co-initiated ROP rac-lactide forming atactic alcohol- or amine-terminated polylactide H-[PLA]-XBn (X = O or NH) with reasonable control of molecular weight via an activated monomer propagation mechanism. Kinetic studies for BnNH2 found the unusual rate expression -d[LA]/dt = k(p(Ae))[2 or 4]0[rac-LA](2)[BnNH2]0(2.5) (k(p(Ca)) ≈ 1.7 ×k(p(Sr))). Preliminary studies suggest that [Y(DBP)3(THF)2] also catalyses amine or alcohol co-initiated ROP by an activated monomer mechanism without loss of a phenoxide ligand.
Decarboxylation syntheses of some polyfluorophenyl -tin and -germanium compounds
Publisher: Elsevier BV
Date: 07-1977
The reactions of metal complexes with alkyl halides—I Reactions of halo(triphenylphosphine)mercury(II) and quaternary halomercurate(II)complexes
Publisher: Elsevier BV
Date: 1962
Transition metal complexes of the small cyano anion dicyanonitromethanide [C(CN)2(NO2)]−
Publisher: Elsevier BV
Date: 11-2013
Organoamidometallics. II. Decarboxylation Syntheses and Structures of [N,N-Dimethyl-N'-(Polyfluorophenyl)Ethane-1,2-Diaminato(1-)]Platinum(II) Complexes
Publisher: CSIRO Publishing
Date: 1988
DOI: 10.1071/CH9880943
Abstract: The complexes Pt[N(p-HC6F4)CH2CH2NMe2]X(L) (L = py , X = Cl or Br L = 2- methylpyridine or 4-methylpyridine, X = Cl ) have been prepared by decarboxylation reactions between PtX2( dmen ) ( dmen = N,N- dimethylethane - 1,2-diamine) and thallous pentafluorobenzoate in the appropriate hot pyridine. Other organoamidoplatinum (II) complexes, Pt[N(R)CH2CH2NMe2] X( py ) (R = p-HC6F4, X = I R = C6F5, X = Cl , Br or I R = p-MeC6F4, X = Cl R = p-ClC6F4 or p-BrC6F4, X = I) and Pt[N(R)CH2CH2NMe2] Cl ( dmpy ) (R = p-HC6F4 dmpy = 2,5-dimethylpyridine), have been prepared by analogous decarboxylations between PtX2( dmen ), thallous 2,3,5,6- tetrafluorobenzoate, and the corresponding polyfluorobenzene, RF. The mixed halogen complex Pt[N(C6F5)CH2CH2NMe2]I0.63Cl0.37( py ) has been prepared similarly and the crystal structure determined. This shows square-planar stereochemistry with the halogen and pyridine trans to NC6F5 and NMe2 respectively. Comparison of spectroscopic data suggests the other complexes have similar stereochemistry.
Direct Syntheses and Structural Novelty of Lanthanoid Aryloxides with Flexible Radial Arms
Publisher: Wiley
Date: 10-2005
Abstract: Direct treatment of excess lanthanum, europium or ytterbium metal with 2,6‐dibenzylphenol (HOdbp) at 150 °C afforded [La 2 (Odbp) 6 ], [Eu 2 (Odbp) 4 ] and [Yb(Odbp) 2 ] n , respectively, in high yields. Alternatively, treatment of Yb metal with excess HOdbp gave an ytterbium( III ) species [Yb 2 (Odbp) 6 ], similar to the lanthanum analogue. X‐ray crystal structures were obtained for [La 2 (Odbp) 6 ], [Eu 2 (Odbp) 4 ] and [Yb 2 (Odbp) 6 ]. [La 2 (Odbp) 6 ] and [Yb 2 (Odbp) 6 ] are pseudo‐centrosymmetric dimers with two terminal and four bridging Odbp – ligands and [Eu 2 (Odbp) 4 ] crystallizes as a centrosymmetric dimer with further organization in a polymeric form through supramolecular interactions. All three structurally characterized compounds achieve coordination saturation by Ln–π‐arene interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Linkage isomerism in phenylmercuric benzene-sulfinate
Publisher: American Chemical Society (ACS)
Date: 1968
DOI: 10.1021/JA01004A051
Pyrazolates advance cerium chemistry: a CeIII/CeIV redox equilibrium with benzoquinone
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7DT00635G
Abstract: Homoleptic Ce IV and Ce III 3,5-dimethylpyrazolate (L) complexes react with 1,4-hydroquinone (H 2 hq) and 1,4-benzoquinone (bq), respectively, to form a new O 2 N 2 diolato ligand (phcd) by means of a Ce III /Ce IV redox equilibrium.
Engineering of Efficient Panchromatic Sensitizers for Nanocrystalline TiO2-Based Solar Cells
Publisher: American Chemical Society (ACS)
Date: 02-2001
DOI: 10.1021/JA003299U
Abstract: A new series of panchromatic ruthenium(II) sensitizers derived from carboxylated terpyridyl complexes of tris-thiocyanato Ru(II) have been developed. Black dye containing different degrees of protonation [(C(2)H(5))(3)NH][Ru(H(3)tcterpy)(NCS)(3)] 1, [(C(4)H(9))(4)N](2)[Ru(H(2)tcterpy)(NCS)(3)] 2, [(C(4)H(9))(4)N](3)[Ru(Htcterpy)(NCS)(3)] 3, and [(C(4)H(9))(4)N](4)[Ru(tcterpy)(NCS)(3)] 4 (tcterpy = 4,4',4' '-tricarboxy-2,2':6',2' '-terpyridine) have been synthesized and fully characterized by UV-vis, emission, IR, Raman, NMR, cyclic voltammetry, and X-ray diffraction studies. The crystal structure of complex 2 confirms the presence of a Ru(II)N6 central core derived from the terpyridine ligand and three N-bonded thiocyanates. Intermolecular H-bonding between carboxylates on neighboring terpyridines gives rise to 2-D H-bonded arrays. The absorption and emission maxima of the black dye show a bathochromic shift with decreasing pH and exhibit pH-dependent excited-state lifetimes. The red-shift of the emission maxima is due to better pi-acceptor properties of the acid form that lowers the energy of the CT excited state. The low-energy metal-to-ligand charge-transfer absorption band showed marked solvatochromism due to the presence of thiocyanate ligands. The Ru(II)/(III) oxidation potential of the black dye and the ligand-based reduction potential shifted cathodically with decreasing number of protons and showed more reversible character. The adsorption of complex 3 from methoxyacetonitrile solution onto transparent TiO(2) films was interpreted by a Langmuir isotherm yielding an adsorption equilibrium constant, K(ads), of (1.0 +/- 0.3) x 10(5) M(-1). The amount of dye adsorbed at monolayer saturation was (n(alpha) = 6.9 +/- 0.3) x 10(-)(8) mol/mg of TiO(2), which is around 30% less than that of the cis-di(thiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) complex. The black dye, when anchored to nanocrystalline TiO(2) films achieves very efficient sensitization over the whole visible range extending into the near-IR region up to 920 nm, yielding over 80% incident photon-to-current efficiencies (IPCE). Solar cells containing the black dye were subjected to analysis by a photovoltaic calibration laboratory (NREL, U.S.A.) to determine their solar-to-electric conversion efficiency under standard AM 1.5 sunlight. A short circuit photocurrent density obtained was 20.5 mA/cm(2), and the open circuit voltage was 0.72 V corresponding to an overall conversion efficiency of 10.4%.
The effect of lewis acids on the thallation of polyfluoroarenes
Publisher: Elsevier BV
Date: 1980
Preparations of organonickel compounds by thermal decomposition of nickel carboxylates
Publisher: CSIRO Publishing
Date: 1972
DOI: 10.1071/CH9722095
Abstract: The carboxylatonickel(11) compounds, (RCO2)2 NiL,αH2O [R = C6F5, p- MeOC6F4, or p-EtOC6F4 L = 2,2'-bipyridyl (bipy), α = 2, or L = 1,l0-hen-anthroline (phen), α = 1], have been obtained from reactions of nickel carbonate, the appropriate carboxylio acids, and the bidentate nitrogen ligands in aqueous ethanol. Nickel has octahedral stereochemistry, and possible structures are discussed. Decomposition of the complexes in boiling toluene, except for C6F5CO2)2X(phen),H2O when boiling benzene with added benzoyl peroxide was used, gave the corresponding organonickel compounds, R2NiL. The formation of the α-substituted phenanthroline derivatives, R2NiL'[R = p-MeOC6F4 or p-EtOC6F4 L' = 2-(p-alkoxytetrafluorophenyl)-1,l0-phenanthroline] and (p-MeOC6F4),NiL" [L" = 2,9-bis(p-methoxytetrafluorophenyl)-1,l0-phenanthroline], accompanied the preparations of the appropriate R2NiL compounds. The stereochemistry of nickel in the organonickel derivatives is approximately planar.
Assembly of 3‐D Network Structures Containing Oxydiacetate and CeIII or CeIV
Publisher: Wiley
Date: 2003
Organoamido- and Aryloxo-lanthanoids. XII. The Coordination Chemistry of Bis(2-phenylindol-1-yl)ytterbium(II), and the X-Ray Crystal Structures of Yb(pin)2(diglyme)(thf) and [Yb(pin)2(dme)]2 (pin = 2-
Publisher: CSIRO Publishing
Date: 1995
DOI: 10.1071/CH9951933
Abstract: With the facile displacement being utilized of thf from Yb(pin)2(thf)4 (pin = 2-phenylindol-1-yl, thf = tetrahydrofuran) in toluene solution, the complexes Yb(pin)2(dme)2 (dme = 1,2- dimethoxyethane), Yb(pin)2 (tmen)(tmen = N,N,N′,N′-tetramethylethane-1,2-diamine) and Yb(pin)2(diglyme)(thf) (diglyme = bis(2-methoxyethyl) ether) have been prepared from the respective ligands and Yb(pin)2(thf)4. Yb(pin)2 (diglyme) (thf) [monoclinic, space group P 21 /c, a 15.35(1), b 16.179(5), c 14.45(2) Ǻ, β 107.51(8)°, Z 4, R 0.044 for 2956 (I 3σ(I)) 'observed' reflections] has a monomeric six-coordinate structure with transoid nitrogen donor atoms, N-Yb-N 143.6(4)° and an irregular coordination polyhedron described as either a distorted trigonal prism or a monocapped square pyramid. Attempted crystallization of Yb(pin)2 (thf) by partial desolvation of Yb(pin)2(thf)4 in hot toluene, containing a trace of dme, gave a mixture of red Yb(pin)2(thf) and orange [Yb(pin)2(dme)]2. The latter was independently synthesized by partial desolvation of Yb(pin)2(dme)2 in toluene. An X-ray crystal structure showed [Yb(pin)2(dme)]2 [monoclinic, space group P 21/c, a 11 .614(2), b 15.945(7), c 15.327(4) Ǻ, β 110.19(2)°, Z 2 dimers, R 0.070 for 2314 (I ≥ 3σ(I)) 'observed' reflections] to be a dimer with two bridging pin ligands, coordinated through nitrogen only. There is an approximately square pyramidal five-coordinate ytterbium environment with an apical dme oxygen, and with two bridging nitrogens, a terminal nitrogen, and a dme oxygen in the basal plane.
Some effects of trifluoromethanesulphonic acid on mercuration in trifluoroacetic acid
Publisher: Elsevier BV
Date: 08-1980
Organolanthanoids. XI. The Crystal and Molecular Structures of Two Tris(η5-cyclopentadienyl)(pyridine) lanthanoid(III) Compounds
Publisher: CSIRO Publishing
Date: 1987
DOI: 10.1071/CH9870907
Abstract: The crystal structures of tris (η5-cyclopentadienyl) (pyridine) samarium(III), monoclinic, space group P21/c, a 10.906(4), b 8.636(2), c 17.825(3) �, β 96.44(2)�, Z 4, R 0.027 and Rw 0.032 for 3619 'observed' reflections, and tris (η5-cyclopentadienyl)(pyridine)neodymium(III), monoclinic, space group P21 / c, a 14-206(4), b 8.619(2), c 15.190(7) �, β 107.38(2)�, Z 4, R 0.035 and R, 0.039 for 2677 'observed' reflections have been determined. Both compounds have pseudotetrahedral geometry with a coordination number of 10 for the lanthanoid metal but there is a difference in the coordination of pyridine and in unit cell packing between the two structures.
Organothallium compounds
Publisher: Elsevier BV
Date: 11-1968
Organoamido- and Aryloxo-Lanthanoids. II. Preparation of Tris(2,6-diphenylphenoxo)-lanthanoid(III) Complexes and the X-Ray Structures of Low-Coordinate [Yb(O-2,6-Ph2C6H3)3] Containing an Intramolecula
Publisher: CSIRO Publishing
Date: 1990
DOI: 10.1071/CH9901245
Abstract: Bulky monomeric lanthanoid(III) aryl oxides Ln(Odpp)3(Odpp = 2,6- diphenylphenoxide Ln = Nd, Sm, Er, Yb or Lu) have been prepared by reaction between the lanthanoid metal, Hg(C6F5)2, and HOdpp in tetrahydrofuran (thf), and Yb(Odpp)3 has also been obtained from an analogous reaction of (PhCC)2Hg. Cleavage of Ln(η5-C5H5)3 (Ln = Nd or Yb) with HOdpp also yields Ln(Opdd)3. The aryl oxides have been isolated as [Ln(Odpp)3(thf)2] (Ln = Nd, Sm or Yb) or as the homoleptic complexes Ln(Odpp)3 (Ln = Nd, Er, Yb or Lu). The X-ray crystal structure of [Yb(Odpp)3(thf)2].thf [crystals monoclinic, space group P21/n, a 11.009(4), b 32.134 (7), c 15.498(6)Ǻ, β 96.72(3)°, Z 4 2785 data refined to R 0.039] shows the complex to have distorted square pyramidal stereochemistry with apical and transoid basal Odpp ligands, (Yb-Odpp) 2.078(9)Ǻ, and transoid basal thf ligands, {Yb-O(thf)} 2.305(8)Ǻ. Similarly, Yb(Odpp)3 [crystals triclinic, space group Pī, a 15.934(2), b 13.563(1), c 10.968(2)Ǻ, α 116.71(1), β 92.90(2), γ 103.38(1)°, Z 2 6236 data refined to R 0.031] was shown to have a trigonal pyramidal arrangement of oxygen donor atoms [{Yb-O} 2.065(4) Ǻ {O-Yb-O} 117.5(1)°], a novel intramolecular chelate Yb…π-arene interaction, {Yb...C} 2.978(6)Ǻ, and an agostic Yb…CH interaction.
Mercury—mercury spin—spin coupling in an organomercury compound
Publisher: Elsevier BV
Date: 12-1984
Structure, Magnetic Behavior, and Anisotropy of Homoleptic Trinuclear Lanthanoid 8-Quinolinolate Complexes
Publisher: American Chemical Society (ACS)
Date: 12-02-2014
DOI: 10.1021/IC402672M
Abstract: Three complexes of the form [Ln(III)3(OQ)9] (Ln = Gd, Tb, Dy OQ = 8-quinolinolate) have been synthesized and their magnetic properties studied. The trinuclear complexes adopt V-shaped geometries with three bridging 8-quinolinolate oxygen atoms between the central and peripheral eight-coordinate metal atoms. The magnetic properties of these three complexes differ greatly. Variable-temperature direct-current (dc) magnetic susceptibility measurements reveal that the gadolinium and terbium complexes display weak antiferromagnetic nearest-neighbor magnetic exchange interactions. This was quantified in the isotropic gadolinium case with an exchangecoupling parameter of J = -0.068(2) cm(-1). The dysprosium compound displays weak ferromagnetic exchange. Variable-frequency and -temperature alternating-current magnetic susceptibility measurements on the anisotropic cases reveal that the dysprosium complex displays single-molecule-magnet behavior, in zero dc field, with two distinct relaxation modes of differing time scales within the same molecule. Analysis of the data revealed anisotropy barriers of Ueff = 92 and 48 K for the two processes. The terbium complex, on the other hand, displays no such behavior in zero dc field, but upon application of a static dc field, slow magnetic relaxation can be observed. Ab initio and electrostatic calculations were used in an attempt to explain the origin of the experimentally observed slow relaxation of the magnetization for the dysprosium complex.
Selective Oxidation of a Single Metal Site of Divalent Calix[4]pyrrolide Compounds [Ln2(N4Et8)(thf)4] (Ln = Sm or Eu), Giving Mixed Valent Lanthanoid(II/III
Publisher: American Chemical Society (ACS)
Date: 10-11-2022
DOI: 10.1021/ACS.INORGCHEM.2C03172
Abstract: The samarium(II) calix[4]pyrrolide complex [Sm
Sulphur dioxide insertion into a cobalt(III)-carbon bond
Publisher: Elsevier BV
Date: 12-1968
Metal–π Interactions Dominate in the Solid‐State Structures of Molecular Heterobimetallic Alkali‐Metal–Europium(II) Aryloxo Complexes
Publisher: Wiley
Date: 29-07-2009
Abstract: Treatment of Eu metal, 2,6-diphenylphenol (HOdpp), and MOdpp (M=Na, K) at elevated temperature in the presence of mercury afforded heterobimetallic complexes which were structurally characterized after crystallization from toluene. The structures of [MEu(Odpp)(3)]nPhMe (M=Na, n=1, 1 K, n=2.5, 2) consist solely of bridging aryloxide ligands and feature extensive pi-Ph-metal interactions. Rather than a heterobimetallic species, treatment of Eu metal and HOdpp with LiOdpp under similar conditions afforded a number of products, including a mixed-valent europium complex, [Eu(2)(Odpp)(3)][Eu(Odpp)(4)]4 PhMe (3). The structural framework of the [Eu(2)(Odpp)(3)](+) cation of 3 is similar to that of the molecular heterobimetallics 1 and 2, including the presence of pi-Ph-Eu interactions. The reluctance of the reaction to provide a Eu/Li heterobimetallic complex was exemplified by the simultaneous crystallization of [Eu(2)(Odpp)(4)]PhMe (6) and the homoleptic cubane [Li(4)(Odpp)(4)]2 C(6)H(14) (5) from toluene/hexane.
A New Method of Synthesis of Monomeric Aryloxide Complexes of Manganese(II): Structures of Manganese Phenoxides
Publisher: Wiley
Date: 30-07-2010
Organomercury compounds
Publisher: Elsevier BV
Date: 09-1981
The far infrared spectra of tetrahalogenozincate(II) complexes with mixed halide ligands
Publisher: CSIRO Publishing
Date: 1967
DOI: 10.1071/CH9672069
Abstract: The far infrared spectra (400-40 cm-1) of the complexes (MePh3As)2 ZnBrnCl4-n (n = 0, 1, 2, 3, or 4), (Et4N)2ZnBrnCl4-n (n = 1, 2, or 3), (Me4N)2ZnBr2Cl2, (pyH)2ZnBr2Cl2, (Et4N)2ZnBrnI4-n (n = 0, 1, 2, 3, or 4), and (Et4N)2ZnClnI4-n (n = 1 or 2) have been recorded. Vibrational assignments have been made for the zinc-halogen frequencies and the spectra are discussed in terms of known or probable structures.
Mercury contamination of the Lerderberg River, Victoria, Australia, from an abandoned gold field
Publisher: Elsevier BV
Date: 06-1982
Synthesis and antiproliferative activity of a series of new platinum and palladium diphosphane complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7DT04615D
Abstract: Organometallic complexes with diphosphane, diolefin, and polyfluorinated aryl ligands R were synthesised and tested for antiproliferative activity.
The van der Waals radius of mercury
Publisher: Elsevier BV
Date: 1980
Coordination polymers of transition metals derived from the in situ nucleophilic addition of alcohols to dicyanonitrosomethanide [C(CN)2(NO)]−
Publisher: Elsevier BV
Date: 07-2013
Reactivity of Bulky Formamidinatosamarium(II or III) Complexes with C═O and C═S Bonds
Publisher: American Chemical Society (ACS)
Date: 10-11-2014
DOI: 10.1021/IC502181G
Abstract: The preparation of a new heterobimetallic samarium(II) formamidinate complex and selected reactions of samarium(II) complexes and one samarium(III) formamidinate complex with benzophenone or CS2 are discussed. Treatment of the tris(formamidinato)samarium(III) complex [Sm(DippForm)3] 1 (DippForm = N,N'-bis(2,6-diisopropylphenyl)formamidinate, (CH(NC6H3-(i)Pr2-2,6)2) with potassium graphite in toluene yielded the dark brown heterobimetallic formamidinatosamarium(II) otassium complex [KSm(DippForm)3]n 2. Divalent 2, a Lewis base solvent free homoleptic species, differs significantly from the related heteroleptic formamidinatosamarium(II) complex [Sm(DippForm)2(thf)2] 3 with respect to its constitution, structure, and reactivity toward benzophenone. While 2 reacts giving complex 1, the reaction of 3 with benzophenone generates the highly unusual [Sm(DippForm)2(thf){μ-OC(Ph)═(C6H5)C(Ph)2O}Sm(DippForm)2] (C6H5 = 1,4-cyclohexadiene-3-yl-6-ylidene) 4. The formation of 4 highlights a rare C-C coupling between a carbonyl carbon and the carbon at the para position of a phenyl group of the OCPh2 fragment. An analogous reaction of [Yb(DippForm)2(thf)2] gives an isostructural complex 4Yb. 3 reacts with carbon disulfide forming a light green dinuclear formamidinatosamarium(III) complex [{Sm(DippForm)2(thf)}2(μ-η(2)(C,S):κ(S',S″)-SCSCS2)] 5 through an unusual C-S coupling induced by an amidinatolanthanoid species giving the thioformylcarbonotrithioate ligand. The trivalent organometallic [Sm(DippForm)2(CCPh)(thf)] complex activates the C═O bond of benzophenone by an insertion reaction, forming the light yellow [Sm(DippForm)2{OC(Ph)2C2Ph}(thf)] 6 as a major product and light yellow unsolvated [Sm(DippForm)2{OC(Ph)2C2Ph}] 7 as a minor product. Molecular structures of complexes (2, 4-7) show that κ(N,N') bonding between a DippForm and samarium atom exists in all compounds, but in 2, DippForm also bridges K and Sm by 1κ(N):2κ(N') bonding and two 2,6-diisopropylphenyl groups are η(6)-bonded to potassium.
Direct Determination of Metal Complexes’ Interaction with DNA by Atomic Telemetry and Multiscale Molecular Dynamics
Publisher: American Chemical Society (ACS)
Date: 03-02-2017
DOI: 10.1021/ACS.JPCLETT.7B00070
Abstract: The lack of molecular mechanistic understanding of the interaction between metal complexes and biomolecules h ers their potential medical use. Herein we present a robust procedure combining resonant X-ray emission spectroscopy and multiscale molecular dynamics simulations, which allows for straightforward elucidation of the precise interaction mechanism at the atomic level. The report unveils an unforeseen hydrolysis process and DNA binding of [Pt{N(p-HC
Synthesis, Structures and Reactivity of Lanthanoid(II) Formamidinates of Varying Steric Bulk
Publisher: Wiley
Date: 30-11-2012
Abstract: New reactive, alent lanthanoid formamidinates [Yb(Form)(2)(thf)(2)] (Form=[RNCHNR] R=o-MeC(6)H(4) (o-TolForm 1), 2,6-Me(2)C(6)H(3) (XylForm 2), 2,4,6-Me(3)C(6)H(2) (MesForm 3), 2,6-Et(2)C(6)H(3) (EtForm 4), o-PhC(6)H(4) (o-PhPhForm 5), 2,6-iPr(2)C(6)H(3) (DippForm 6), o-HC(6)F(4) (TFForm 7)) and [Eu(DippForm)(2)(thf)(2)] (8) have been prepared by redox transmetallation rotolysis reactions between an excess of a lanthanoid metal, Hg(C(6)F(5))(2) and the corresponding formamidine (HForm). X-ray crystal structures of 2-6 and 8 show them to be monomeric with six-coordinate lanthanoid atoms, chelating N,N'-Form ligands and cis-thf donors. However, [Yb(TFForm)(2)(thf)(2)] (7) crystallizes from THF as [Yb(TFForm)(2)(thf)(3)] (7a), in which ytterbium is seven coordinate and the thf ligands are "pseudo-meridional". Representative complexes undergo C-X (X=F, Cl, Br) activation reactions with perfluorodecalin, hexachloroethane or 1,2-dichloroethane, and 1-bromo-2,3,4,5-tetrafluorobenzene, giving [Yb(EtForm)(2)F](2) (9), [Yb(o-PhPhForm)(2)F](2) (10), [Yb(o-PhPhForm)(2)Cl(thf)(2)] (11), [Yb(DippForm)(2)Cl(thf)] (12) and [Yb(DippForm)(2)Br(thf)] (16). X-ray crystallography has shown 9 to be a six-coordinate, fluoride-bridged dimer, 12 and 16 to be six-coordinate monomers with the halide and thf ligands cis to each other, and 11 to have a seven-coordinate Yb atom with "pseudo-meridional" unidentate ligands and thf donors cis to each other. The analogous terbium compound [Tb(DippForm)(2)Cl(thf)(2)] (13), prepared by metathesis, has a similar structure to 11. C-Br activation also accompanies the redox transmetallation rotolysis reactions between La, Nd or Yb metals, Hg(2-BrC(6)F(4))(2), and HDippForm, yielding [Ln(DippForm)(2)Br(thf)] complexes (Ln=La (14), Nd (15), Yb (16)).
Chalcogen Bonds in Selenocysteine Seleninic Acid, a Functional GPx Constituent, and in Other Seleninic or Sulfinic Acid Derivatives
Publisher: Wiley
Date: 16-07-2021
Abstract: The controlled oxidation reaction of L‐selenocystine under neutral pH conditions affords selenocysteine seleninic acid (3‐selenino‐L‐alanine) which is characterized also by means of single‐crystal X‐ray diffraction. This technique shows that selenium forms three chalcogen bonds (ChBs), one of them being outstandingly short. A survey of seleninic acid derivatives in the Cambridge Structural Database (CSD) confirms that the C−Se(=O)O− functionality tends to act as a ChB donor robust enough to systematically influence the interactional landscape in the solid. Quantum Theory of Atom in Molecules (QTAIM) analysis proves the attractive nature of the short contacts observed in crystals containing the seleninic functionality and calculation of surface molecular electrostatic potential (MEP) reveals that remarkably positive σ‐holes can frequently be found opposite to the covalent bonds at selenium. Both CSD searches and QTAIM and MEP approaches show that also the sulfinic acid moiety can function as a ChB donor, albeit less frequently than the seleninic acid one. These findings may contribute to a better understanding, at the atomic level, of the mechanism of action of the enzymes that control oxidative stress and ROS deactivation and that contain selenocysteine seleninic acid and cysteine sulfinic acid in the active site.
Additions and Corrections - Linkage Isomerism in Phenylmercuric Benzenesulfinate
Publisher: American Chemical Society (ACS)
Date: 11-1968
DOI: 10.1021/JA01026A600
Metal‐Promoted Nucleophilic Addition and Cyclization of Diamines with Dicyanonitrosomethanide, [C(CN)2(NO)]−
Publisher: Wiley
Date: 28-04-2009
Abstract: The metal-promoted nucleophilic addition of diaminoalkanes to dicyanonitrosomethanide, C(CN)2(NO)- (dcnm), and subsequent cyclization has been utilized in the synthesis of novel anionic species. The addition and cyclization of 1,2-diaminoethane (en) to both nitrile groups of dcnm forms the anion diimidazolinylnitrosomethanide (dinm), isolated in the dinuclear complex [{Cu(dinm)(en)}2en][ClO4]2 (1). The same reaction solution yields [Cu(cinm)(ainm)] (cinm=cyanoimidazolinylnitrosomethanide, ainm=(((2-aminoethyl)amino)iminomethyl)imidazolinylnitrosomethanide) (2), which contains intermediates of the dinm species, supporting a stepwise mechanism of addition of the diamine followed by cyclization. 1,3-Diaminopropane (pn) added and cyclized on only one nitrile group to form a 1,4,5,6-tetrahydropyrimidine ring. This resulted in the formation of the cyanonitroso-1,4,5,6-tetrahydropyrimidinylmethanide ligand (cnpm) in complexes with the general formula [M(cnpm)2(pn)] (M=Cu (3a), Ni (3b), Zn (3c)). These reactions are contrasted to the addition of ethanolamine in the pyridine (py) complex [Ni(chnm)2(py)2].(py) (4) (chnm=cyano((2-hydroxyethyl)amino)iminomethylnitrosomethanide) with no cyclization, demonstrating the higher reactivity of amines compared with alcohols. The formation of the complexes [M(cmnm)2(mame)] (M=Co (5a), Ni (5b), cmnm=cyano(imino(methoxy)methyl)nitrosomethanide, mame=1-dimethylamino-2-methylaminoethane) indicate mame may be too sterically hindered to add to dcnm under similar reaction conditions.
A simple one-pot, multi-component synthesis of cyano-functionalized bis-β-diketones
Publisher: Elsevier BV
Date: 05-2013
η6‐Arene(halogenidoaluminato)lanthanoid(III) Complexes: Synthesis, Characterization and Catalytic Activity for Isoprene Polymerization
Publisher: Wiley
Date: 24-01-2022
Abstract: η 6 ‐Arene(iodido‐/bromido‐aluminato)lanthanoid(III) complexes, [Ln(η 6 ‐C 6 H 5 Me)(AlI 4 ) 3 ] [Ln=La ( 1 ), Ce ( 2 ), Nd ( 3 ), (Gd) ( 4 ) C 6 H 5 Me=toluene], [Ln(η 6 ‐C 6 H 3 Me 3 ‐1,3,5)(AlI 4 ) 3 ] [Ln=La ( 5 ), Ce ( 6 ), Pr ( 7 ), Nd ( 8 ), Sm ( 9 ), Gd ( 10 ) C 6 H 3 Me 3 ‐1,3,5=mesitylene], and [Ln(η 6 ‐C 6 H 5 Me)(AlBr 4 ) 3 ] [Ln=La ( 11 ), Nd ( 12 ), Sm ( 13 )] were prepared by reactions of aluminium triiodide or aluminium tribromide with the corresponding lanthanoid metals and 1,2‐diiodoethane or 1,2‐dibromoethane in an arene (toluene or mesitylene) solution (molar ratio : 6 : 2 : 3). The first X‐ray crystal structures of arene(iodidoaluminato)lanthanoid(III) complexes are reported. The lanthanoid atom is coordinated by an η 6 ‐arene and three chelating κ(I, I′)‐tetraiodidoaluminato ligands. The tetrabromidoaluminate complexes have similar structures. The precatalyst 3 was treated with AlR 3 (R=Me or i Bu) to give [Nd(η 6 ‐C 6 H 5 Me)(AlI 3 R) 3 ] species in situ , which were then tested for catalytic activity towards isoprene polymerization. Although the resulting polyisoprene had a desirable high cis‐ 1,4 content, the catalyst performance was well below known best performing systems and indicates that iodidoaluminates are the least favorable of the halogenidoaluminatolanthanoid(III) complexes.
Oxidation of mercury electrodes in the presence of phenyl-mercury, -lead and -bismuth organometallic compounds in dichloromethane
Publisher: Elsevier BV
Date: 12-1989
A facile and benign synthesis of binuclear ruthenium(I) “sawhorse” complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2000
DOI: 10.1039/B002304N
Tetraethylammonium tetrahalogenozincate(II) complexes with mixed halide ligands
Publisher: Royal Society of Chemistry (RSC)
Date: 1966
DOI: 10.1039/J19660000463
Molecular and Crystal Structures of Pentafluorophenyl‐platinum(II) Complexes with Bis(diphenylphosphino)methane, Bis(diphenylarsino)methane and 1,2‐Bis(diphenylarsino)ethane
Publisher: Wiley
Date: 27-02-2006
Specimens at the Center: An Informatics Workflow and Toolkit for Specimen-level Analysis of Public DNA Database Data
Publisher: American Society of Plant Taxonomists
Date: 09-2016
Synthesis and Structure of New Lanthanoid Carbonate “Lanthaballs”
Publisher: American Chemical Society (ACS)
Date: 28-10-2014
DOI: 10.1021/IC5016115
Abstract: New insights into the synthesis of high-nuclearity polycarbonatolanthanoid complexes have been obtained from a detailed investigation of the preparative methods that initially yielded the so-called "lanthaballs" [Ln(13)(ccnm)(6)(CO(3))(14)(H(2)O)(6)(phen)(18)] Cl(3)(CO(3))·25H(2)O [α-1Ln Ln = La, Ce, Pr phen = 1,10-phenanthroline ccnm = carbamoylcyanonitrosomethanide]. From this investigation, we have isolated a new pseudopolymorph of the cerium analogue of the lanthaball, [Ce(13)(ccnm)(6)(CO(3))(14)(H(2)O)(6)(phen)(18)]·C(l3)·CO(3) (β-1Ce). This new pseudopolymorph arose from a preparation in which fixation of atmospheric carbon dioxide generated the carbonate, and the ccnm ligand was formed in situ by the nucleophilic addition of water to dicyanonitrosomethanide. From a reaction of cerium(III) nitrate, instead of the previously used chloride salt, with (Et4N)(ccnm), phen, and NaHCO(3) in aqueous methanol, the new complex Na[Ce(13)(ccnm)(6)(CO(3))(14)(H(2)O)(6)(phen)(18)](NO(3))(6)·20H(2)O (2Ce) crystallized. A variant of this reaction in which sodium carbonate was initially added to Ce(NO(3))(3), followed by phen and (Et(4)N)(ccnm), also gave 2Ce. However, an analogous preparation with (Me4N)(ccnm) gave a mixture of crystals of 2Ce and the coordination polymer [CeNa(ccnm)4(phen)3]·MeOH (3), which were manually separated. The use of cerium(III) acetate in place of cerium nitrate in the initial preparation did not give a high-nuclearity complex but a new coordination polymer, [Ce(ccnm)(OAc)(2)(phen)] (4). The first lanthaball to incorporate neodymium, namely, [Nd(13)(ccnm)(4)(CO(3))14(NO(3))(4)(H(2)O)(7)(phen)(15)](NO(3))(3)·10H(2)O (5Nd), was isolated from a preparation similar to that of the second method used for 2Ce, and its magnetic properties showed an antiferromagnetic interaction. The identity of all products was established by X-ray crystallography.
Synthesis and Structural Properties of Heteroleptic Rare Earth Mixed Carboxylates with Well‐defined Solvation Spheres
Publisher: Wiley
Date: 20-08-2010
Abstract: Mixed carboxylate complexes of cerium(III) and yttrium(III), [Ce 2 (OAc) 4 (salH) 2 (OH 2 ) 4 ] · 4HOAc and [Y 2 (OAc) 4 (salH) 2 (OH 2 ) 4 ] · 2H 2 sal (HOAc, H 2 sal ≡ acetic, salicylic acids) have been structurally characterized as tetrakis(acetic) and bis(salicylic) acid solvates, respectively. The dinuclear complex components take an identical form: [(OAc‐ O,O ′)(H 2 O) 2 Ln ( O ,μ‐ O ′‐OAc) 2 ( O ‐Hsal‐ O ′) 2 Ln (OH 2 ) 2 ( O , O ′‐OAc)], with bridging pairs of acetate and salicylate ligands. The solvating acid molecules are closely and elegantly associated with the dinuclear complex via hydrogen bonding, these aggregates in turn being held together in the lattice by interactions between water molecule hydrogen atoms and neighboring carboxylate oxygen atoms.
Synthesis and structure of the two-dimensional coordination networks [Ln(PDC)(N-HPDC)]∞ (PDC=pyridine-3,4-dicarboxylate, Ln=La, Ce, Pr)
Publisher: Elsevier BV
Date: 2007
Bismuth(III ) acetate: a cheap, efficient, and environmentally acceptable reagent for ‘wet’ and ‘dry’ prevost reactions
Publisher: Royal Society of Chemistry (RSC)
Date: 1989
DOI: 10.1039/C39890000407
Syntheses and structures of N-polyfluorophenyl- and N,N′-bis(polyfluorophenyl)ethane-1,2-diaminato(1- or 2-)platinum(II) complexes
Publisher: Elsevier BV
Date: 11-2010
A rare earth alloy as a synthetic reagent: contrasting homometallic rare earth and heterobimetallic outcomes
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B600868B
The first neutral homoleptic lanthanoid pyrazolates, including the mixed oxidation state species [Yb2(But2pz)5] (But2pz = 3,5-di-tert-butylpyrazolate), from a simple new synthesis of pyrazolate comple
Publisher: Royal Society of Chemistry (RSC)
Date: 1999
DOI: 10.1039/A902675D
Bromobenzene Transforms Lanthanoid Pseudo‐Grignard Chemistry
Publisher: Wiley
Date: 05-05-2023
Abstract: Divalent lanthanoid pseudo‐Grignard reagents PhLnBr (Ln=Sm, Eu and Yb) can be easily prepared by the oxidative addition of bromobenzene (PhBr) to lanthanoid metals in tetrahydrofuran (THF). PhLnBr reacts with bulky N,N′ ‐bis(2,6‐di‐ iso propylphenyl)formamidine (DippFormH) to generate Ln II complexes, namely [Ln(DippForm)Br(thf) 3 ] 2 ⋅6thf ( 1 Sm , 2 Eu ), and [Yb(DippForm)Br(thf) 2 ] 2 ⋅2thf ( 3 Yb ). Samarium and europium (in 1 and 2 ) are seven coordinate, whereas ytterbium (in 3 ) is six coordinate, and all are bromine‐bridged dimers. When PhLnBr reacts with 3,5‐diphenylpyrazole (Ph 2 pzH), both alent ( 5 [Eu(Ph 2 pz) 2 (thf) 4 ]) and trivalent ( 4 a [Sm(Ph 2 pz) 3 (thf) 3 ]⋅3thf, 4 b [Sm(Ph 2 pz) 3 (dme) 2 ]⋅dme) complexes are obtained. In the monomeric compounds 4 ( a,b ), samarium is nine coordinate but europium is eight coordinate in 5 . The use of PhLnBr in this work transforms the outcomes from earlier reactions of PhLnI.
Divalent metal complexes (Ca, Sr, Ba, Yb) of the unsymmetrical 3-(2′-thienyl)-5-(trifluoromethyl)pyrazolate ligand
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0DT01289K
Abstract: The alent complexes [M(ttfpz)(2)(thf)(4)] (ttfpz = 3-(2'-thienyl)-5-(trifluoromethyl)pyrazolate M = Yb, 1, Ca, 2, Sr, 3, Ba, 4 thf = tetrahydrofuran) and [M(ttfpz)(2)(dme)(n)] (M = Ca, 5, Sr, 6, Yb, 7, n = 2 M = Ba, 8, n = 3 dme = 1,2-dimethoxyethane) have been prepared by redox transmetallation rotolysis reactions employing the free metals, Hg(C(6)F(5))(2) and ttfpzH in donor solvents and their structures determined. The monomeric structures exhibit η(2)-bound pyrazolate ligands with eight-coordinate metal atoms for complexes 1-7 and a ten-coordinate metal for 8. The pyrazolate ligands in the thf-complexes 1-4 as well as dme-derivatives 5 and 6 are in a transoid configuration, whilst in complex 7 the ttfpz ligands exhibit a cisoid relationship. In 8 the ligands have an intermediate role in between cisoid and transoid.
Oxidation of the Platinum(II) Anticancer Agent [Pt{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] to Platinum(IV) Complexes by Hydrogen Peroxide
Publisher: MDPI AG
Date: 09-2023
Preparation and Structures of Rare Earth 3-Benzoylpropanoates and 3-Phenylpropanoates
Publisher: CSIRO Publishing
Date: 2020
DOI: 10.1071/CH20197
Abstract: Rare earth (RE) complexes of 3-benzoylpropanoate (bp), [RE(bp)3(H2O)n] (RE=La, n=2 RE=Y, Ce, Pr, Nd, Yb, n=1) and 3-phenylpropanoate (pp), [RE(pp)3] (RE=Y, La, Ce, Nd, Yb), have been prepared by metathesis reactions between the corresponding rare earth chloride and the appropriate sodium carboxylate. Analysis by single-crystal X-ray diffraction finds that both RE bp and pp complexes favour formation of carboxylate-bridged 1-D coordination polymers in the solid state. Here, the former favours heteroleptic 9 or 10-coordinate complexes (splitting between Ce and La) with the carbonyl remaining uncoordinated but participating as a hydrogen bond acceptor with water in the coordination sphere. Lack of bp carbonyl coordination leaves this group available for surface interactions during corrosion inhibition and complex solubilization. The latter pp derivatives form eight-coordinate complexes for Y and Yb and are the first ex les of homoleptic RE pp complexes to be reported.
Decarboxylation syntheses of transition metal organometallics
Publisher: Elsevier BV
Date: 08-1987
Synthesis and magnetic properties of a series of 3d/4f/3d heterometallic trinuclear complexes incorporating in situ ligand formation
Publisher: Elsevier BV
Date: 07-2012
Synthesis and Structural Characterization of 1,2‐Benzenedisulfonate Complexes of the Heavy Group 2 Elements
Publisher: Wiley
Date: 05-2009
Abstract: Reaction of the commercially available potassium 1,2‐benzenedisulfonate (K 2 L) with calcium chloride, strontium nitrate, and barium chloride in aqueous solution yielded [Ca 2 L 2 (H 2 O) 4 ], [Sr 4 L 4 (H 2 O) 8 ] · 1.5H 2 O and [Ba 2 L 2 (H 2 O) 5 ] · H 2 O in a form suitable for single‐crystal X‐ray determination. From one preparation of the calcium complex a few crystals of [K 2 CaL 2 (H 2 O) 3 ] · 0.5H 2 O were obtained but were not representative of the bulk product. From reaction of CaCO 3 with H 2 L and recrystallization from aqueous ethanol, crystals of [Ca 2 L 2 (H 2 O) 6 ] · EtOH deposited. All complexes are coordination polymers with metal atoms being bridged and chelated by 1,2‐benzenedisulfonate groups, which show an enormous variety of coordination modes, and coordinated by water molecules, some of which are bridging. Calcium has an eight‐coordinate ion in all compounds, potassium six‐coordinate in the bimetallic complex the strontium complex has eight‐ and nine‐coordinate strontium atoms and the barium complex nine‐ and eleven‐coordinate barium atoms.
In situ ligand formation in the synthesis of an octanuclear dysprosium ‘double cubane’ cluster displaying single molecule magnet features
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT11905F
Abstract: The nucleophilic addition of methanol and water to the dicyanonitrosomethanide anion, resulting in the formation of cyano(imino(methoxy)methyl)nitrosomethanide (cmnm) and carbamoylcyanonitrosomethanide (ccnm), respectively, is used as a means of in situ ligand synthesis during the formation of [Dy(8)(OH)(6)(OMe)(6)(cmnm)(10)(ccnm)(2)(H(2)O)(2)(MeOH)(2)] (1). This is the first time these reactions have been observed to be promoted by the presence of a lanthanoid ion. The core of the octanuclear cluster consists of two cubane moieties ([Dy(4)(OH)(3)(OMe)]), bridged by four methoxide ligands to form a central [Dy(8)(OH)(6)(OMe)(6)] moiety. The complex displays magnetic properties that are indicative of probable single molecule magnet features.
High temperature synthesis of some strontium and barium 2,6-dibenzylphenolates
Publisher: Elsevier BV
Date: 2007
Effect of charge and surface area on the cytotoxicity of cationic metallointercalation reagents
Publisher: Canadian Science Publishing
Date: 06-2005
DOI: 10.1139/V05-110
Abstract: Reaction of a series of nitrogen donor ligands (1-phenylpyrazoles, 2-phenylpyridine, benzo[h]quinoline, 1-(2′-pyridyl)indole, 1-phenylindazole, and 2-phenylindazole) with palladium(II) and platinum(II) salts gave complexes where ortho-metallation had occurred resulting in bidentate binding to the metal centres through N and C atoms. These cyclometallated products were isolated as µ-chloro dimers. Subsequent treatment of these µ-chloro dimers with chelating diamines such as 1,2-ethanediamine converted them into 14 cationic (1+) complexes. Analogous coordination mixed ligand complexes (charge 2+) were prepared by reaction of dichloro(1,2-ethanediamine-N,N′)palladium(II) with aromatic diamines such as 2-(1′-pyrazolyl)pyridine, 2,2′-bipyridine, and 1,10-phenanthroline. The complexes exhibited growth inhibitory activity against L1210 mouse leukæmia cells in vitro over a wide concentration range in general, the cyclometallated complexes were more active than the mixed ligand complexes, although one cyclometallated organoplatinum complex was less active than the mixed ligand analogue. Substitution around the periphery of the aromatic ligands also resulted in increased activity. One complex, derived from 1-(2'-pyridyl)indole, was tested in vivo and showed no significant antitumour inhibition against P388 leukæmia at doses below toxic levels. Key words: anticancer, metallointercalator, cyclometallation, palladium, platinum, cytotoxicity.
New decarboxylation syntheses of polyfluorophenylorganometallic compounds
Publisher: Elsevier BV
Date: 12-1976
Synthesis and crystal structure of [N,N′-bis(2,3,5,6-tetrafluorophenyl)-ethane-1,2-diaminato(2-)]dipyridineplatinum(II)
Publisher: Elsevier BV
Date: 1984
New Interventions by silicone grease in synthesis
Publisher: Wiley
Date: 24-08-2022
Abstract: In redox‐transmetallation protolysis (RTP) reactions in tetrahydrofuran (thf) between excess scandium or cerium metal, Hg(C 6 F 5 ) 2 and 3,5‐dimethylpyrazole (Me 2 pzH) in silicone greased Schlenk flasks, formation of the 3,5‐dimethyl‐1‐pyrazolyl(dimethyl)siloxide (Me 2 pzSiMe 2 O) ligand was observed. Thus the former reaction gave [Sc 2 (Me 2 pz) 4 (Me 2 pzSiMe 2 O) 2 ] 1 in good yield, whilst the latter gave a mixture of [Ce 4 O(Me 2 pz) 9 (Me 2 pzSiMe 2 O) 2 ] 2 a , [Ce 4 O(Me 2 pz) 11 ] 2 b , both mixed oxidation state species, and the Ce IV complex [Ce(Me 2 pz) 4 (Me 2 pzH)] 2 c .
Organothallium compounds
Publisher: Elsevier BV
Date: 04-1970
Mono‐, Di‐, Tri‐ and Tetranuclear Rare Earth Complexes Obtained Using a Moderately Bulky Aryloxide Ligand
Publisher: Wiley
Date: 28-10-2009
Organomercury compounds. XIV. The preparations of bispolychlorophenylmercury compounds by mercuration reactions
Publisher: CSIRO Publishing
Date: 1972
DOI: 10.1071/CH9721645
Abstract: The bispolychlorophenylmercurials R2Hg (R = C6Cl5 2,3,4,5-Cl4H, 2,3,4,6- Cl4C6H 2,3,5,6-C14C6H, 2,3,4-Cl3C6H2, 2,4,6-Cl2C6H2, and 2,5-Cl2C6H3) have been prepared by direct mercuration of pentachlorobenzene, 1,2,3,4-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene, 1,2,4,5-tetraohlorobenzene, 1,2,3-trichlorobenzene, 1,3,5-trichlorobenzene, and 1,4-dichlorobenzene respectively, with mercuric trifluoroacetate at elevated temperatures. Similar syntheses of bispentachlorophenylmercury from mercuric difluoroacetate and fluoroacetate have also been carried out. From merouration of pentaohlorobenzene with mercuric trifluoroaoetate and difluoroacetate under milder conditions, pentachlorophenylmercuric trifluoroacetate and difluoroacetate have been obtained. The former undergoes thermal decomposition into bispenta chlorophenylmercury and mercuric trifluoroacetate.
Permercurated arenes. III. Syntheses of periodoarenes and perchloroarenes by Iodo- and Chloro-demercuration of some permercurated arenes
Publisher: CSIRO Publishing
Date: 1977
DOI: 10.1071/CH9771701
Abstract: The polyiodobenzenes C6I5X (X = NO2, H, Br, Cl, F, MeO, Me, CO2H or CF3) and hexaiodo-benzene have been prepared in good yield by reaction of triiodide ions with suitable permercurated arenes in dimethylformamide at room temperature. Mass and/or p.m.r. spectra showed that singly recrystallized s les of C6I5X (X = NO2, Br, Cl, F or CF3) contained minor amounts of the corresponding tetraiodobenzenes C6HI4X. In cases where further recrystallization failed to remove the partially iodinated species, purer products could be obtained from permercurated arenes prepared using increased Hg(O2CCF3)2/substrate ratios. The polychlorobenzenes C6Cl5X (X = NO2, H, Br, F, MeO, Me or CO2H) and hexachlorobenzene have been prepared by reaction of chlorine with solutions or suspensions of the appropriate permercurated benzenes in dimethylformamide at room temperature. Attempted permercuration of naphthalene followed by chlorodemercuration gave perchloronaphthalene containing a substantial impurity of heptachloronaphthalene. Permercuration of sodium p-toluenesulphinate was accompanied by complete desulphination giving permercurated toluene.
The formation of mercurycarbon bonds by sulphur trioxide elimination
Publisher: Elsevier BV
Date: 02-1971
Ruthenium carbonyl complexes. III. Peparations, properties and structures of Dicarbonyl- and Monocarbonyl-(2,2':6',2''-terpyridyl)ruthenium(II) complexes
Publisher: CSIRO Publishing
Date: 1984
DOI: 10.1071/CH9840929
Abstract: Reaction of 2,2':6',2''-terpyridyl (tpy) with ruthenium dicarbonyl dihalides yields the complexes Ru(CO)2X2(tpy) (X = Br or Cl), which can be protonated giving [Ru(CO)2X2(tpyH)]ClO4. Crystal structures of the two forms (red and yellow) of Ru(CO)2Br2(tpy) show each to have octahedral stereo-chemistry with cis-carbonyls, trans-bromines, and bidentate tpy. Treatment of Ru(CO)2X2(tpy) complexes with trimethylamine N-oxide in dichloromethane at room temperature gives cis-Ru(CO)X2(tpy) complexes. The presence of cis halogens and tridentate terpyridyl in the chloro complex has been established by X-ray crystallography. Reaction of terpyridyl with ruthenium trichloride in dimethylformamide yields trans-Ru(CO)Cl2(tpy), the crystal structure of which has been determined.
Unique and contrasting structures of homoleptic lanthanum(iii) and cerium(iii) 3,5-dimethylpyrazolates.
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8DT00338F
Abstract: Homoleptic [La(Me2pz)3]n (Me2pz = 3,5-dimethylpyrazolato) is a μ-η2:η5-Me2pz coordination polymer with 12-coordinate La atoms in an unusual η5:η5 Me2pz sandwich, whilst the cerium congener forms a molecular tetrametallic cage [Ce4(Me2pz)12] featuring six different Me2pz coordination modes.
On the reaction mechanism of redox transmetallation of elemental Yb with Hg(C6F5)2 and subsequent reactivity of Yb(C6F5)2 with pyrazol
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5CC05439G
Abstract: DFT investigations of the redox transmetallation reaction of the diorganomercurial (Hg(C 6 F 5 ) 2 ) with Yb metal, yielding Yb(C 6 F 5 ) 2 , allowed us to define a very low energy reaction mechanism via a C 6 F 5 Yb–HgC 6 F 5 intermediate.
The synthesis and structures of rare earth 2-fluorophenyl- and 2,3,4,5-tetrafluorophenyl-N,N′-bis(aryl)formamidinate complexes
Publisher: Elsevier BV
Date: 2016
Solvothermal vs. bench-top reactions: Control over the formation of discrete complexes and coordination polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B707709B
Abstract: The formation of discrete complexes [M(mcoe)2S2] (M = Cu, Ni S = MeOH, H2O) vs. a nitroso-bridged ferromagnetically-coupled Cu(II) coordination polymer [Cu(mcoe)2] is influenced by the use of solvothermal reaction conditions.
Bulky Group 2 Octaphenylmetallocenes and Direct Access to Calcium and Ytterbium Pseudo-Grignard Complexes
Publisher: American Chemical Society (ACS)
Date: 26-12-2014
DOI: 10.1021/OM501150B
Structural and anticancer properties of hydrogen bonded diphenyl phosphate adducts of Pt(IV) complexes: The importance of pKa matching
Publisher: Elsevier BV
Date: 10-2012
DOI: 10.1016/J.JINORGBIO.2012.04.010
Abstract: Co-crystallisation of diphenyl phosphate (Hdpp) with anticancer active Pt(IV) complexes of the type cis,trans,cis-[PtCl(2)(OH)(2)(am(m)ine)(2)] has produced a new type of supramolecular adduct with short hydrogen bonds from the Hdpp molecules to the hydroxide ligands in all cases. X-ray crystallographic analysis showed within the adduct cis,trans-[PtCl(2)(en)(OH(2))(2)](dpp)(2) (1) a hydrogen bond length of 2.341(6) Å the shortest O ··· O distance reported in the literature. Similar, though longer hydrogen bonds were observed in three other complexes: [PtCl(2)(OH)(NH(3))(2)(OH(2))]dpp·3H(2)O (2), trans-[Pt(mal)(OH)(OH(2))(S,S-chxn)]dpp·3H(2)O (3), and trans-[Pt(ox)(OH)(OH(2))(S,S-chxn)]dpp·2H(2)O (4). Co-crystallisation with Hdpp leads to higher aqueous solubility than the parent complexes indicating the potential of the adducts for use as active pharmaceutical ingredients. Anticancer testing of [Pt(mal)(OH)(OH(2))(S,S-chxn)]dpp·3H(2)O (3) showed in vitro cytotoxicity is low, as expected for Pt(IV) prodrugs, yet substantial tumour growth inhibition was observed in an in vivo ADJ/PC6 tumour model, with activity retained at maximum tolerated dose (MTD)/2 and MTD/4.
Structural Variety in Solvated Lanthanoid(III ) Halide Complexes
Publisher: CSIRO Publishing
Date: 2000
DOI: 10.1071/CH00117
Abstract: Treatment of lanthanum metal with CH2Br2 or CH2I2 in tetrahydrofuran (thf) under ultrasound conditions yields the corresponding [LaX3(thf)4] (X = Br, I) complexes in good yield. Recrystallization of [LaBr3(thf)4] from 1,2-dimethoxyethane (dme) or bis(2-methoxyethyl) ether (diglyme) generates [LaBr2(µ-Br)(dme)2]2 and [LaBr2(dig-lyme)2][LaBr4(diglyme)]. Treatment of lanthanoid metals with hexachloroethane in dme yields [LnCl3(dme)2] (Ln = La, Nd, Er or Yb) and in acetonitrile [YbCl2(MeCN)5]2[YbCl3(MeCN)(-Cl)2YbCl3(MeCN)]. The reaction of Yb metal pieces with 1,2-dibromoethane in thf and dme gave single crystals of [YbBr3(thf)3] and [YbBr3(dme)2], respectively. The X-ray determined structure of [LaBr3(thf)4] shows a seven-coordinate monomer with pentagonal-bipyramidal stereochemistry and apical bromide ligands. For [YbBr3(thf)3], a monomeric structure with mer-octa-hedral stereochemistry is observed. In [LaBr2(µ-Br)(dme)2]2, two eight-coordinate La centres are linked by two bridging bromides. The dme ligands have a trans relationship to each other, and cis terminal bromides are transoid to the bridging bromides with dodecahedral stereochemistry for La. By contrast, the 1: 1.5 diglyme adduct is found to be ionic [LaBr2(diglyme)2][LaBr4(diglyme)], with an eight-coordinate bicapped trigonal-prismatic lanthanum cation and a seven-coordinate pentagonal-bipyramidal lanthanum anion. In the cation, the bromide ligands are cis to each other, and in the anion, two bromides are equatorial and two are axial. In [YbBr3(dme)2], [YbCl3(dme)2] and [ErCl3(dme)2], a seven-coordinate pentagonal-bipyramidal arrangement exists with apical halogen ligands. Far-infrared data, and in particular the absence of absorptions attributable to Ì(La–Clter), suggest that [LaCl3(dme)] is polymeric with six bridging chlorides per lanthanum. For [YbCl2(MeCN)5]2[YbCl3(MeCN)(-Cl)2YbCl3-(MeCN)], a remarkable ionic structure, with pentagonal-bipyramidal [YbCl2(MeCN)5]+ cations and octahedral di-nuclear [YbCl3(MeCN)(-Cl)2YbCl3(MeCN)]2– counter ions, is observed. In the former, chloride ligands are apical, while the MeCN ligands of the latter are transoid.
Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co‐oxidant Needed?
Publisher: Wiley
Date: 05-11-2015
Abstract: Treatment of N,N'-bis(aryl)formamidines (ArFormH), N,N'-bis(2,6-difluorophenyl)formamidine (DFFormH) or N,N'-bis(2,6-diisopropylphenyl)formamidine (DippFormH), with europium metal in CH3 CN is an efficient synthesis of the alent complexes: [{Eu(DFForm)2 (CH3 CN)2 }2 ] (Eu1) or [Eu(DippForm)2 (CH3 CN)4 ] (Eu2). The synthetic method was extended to ytterbium, but the metal required activation by addition of Hg(0) . With DFFormH in CH3 CN, [{Yb(DFForm)2 (CH3 CN)}2 ] (Yb1) was obtained in good yield, and [Yb(DFForm)2 (thf)3 ] (Yb3) was obtained from a synthesis in CH3 CN/THF. Thus, this synthetic method completely circumvents the use of either salt metathesis, or redox transmetallation rotolysis (RTP) protocols to prepare alent rare-earth formamidinates. Heating Yb1 in PhMe/C6 D6 resulted in decomposition to trivalent products, including one from a CH3 CN activation process. For a synthetic comparison, alent ytterbium DFForm and DippForm complexes were synthesised by RTP reactions between Yb(0) , Hg(R)2 (R=Ph, C6 F5 ), and ArFormH in THF, leading to the isolation of either [Yb(DFForm)2 (thf)3 ] (Yb3), or the first five coordinate rare-earth formamidinate complex [Yb(DippForm)2 (thf)] (Yb4 b), and, from adjustment of the stoichiometry, trivalent [Yb(DFForm)3 (thf)] (Yb6). Oxidation of Yb3 with benzophenone (bp), or halogenating agents (TiCl4 (thf)2 , Ph3 CCl, C2 Cl6 ) gave [Yb(DFForm)3 (bp)] or [Yb(DFForm)2 Cl(thf)2 ], respectively. Furthermore, the structural chemistry of alent ArForm complexes has been substantially broadened. Not only have the highest and lowest coordination numbers for alent rare-earth ArForm complexes been achieved in Eu2 and Yb4 b, respectively, but also dimeric Eu1 and Yb1 have highly unusual ArForm bridging coordination modes, either perpendicular μ-1κ(N:N'):2κ(N:N') in Eu1, or the twisted μ-1κ(N:N'):2κ(N':F') DFForm coordination in Yb1, both unprecedented in alent rare-earth ArForm chemistry and in the wider alent rare-earth amidinate field.
The preparation of adducts of diphenylmercury with bidentate ligands
Publisher: Elsevier BV
Date: 03-1969
Organomercury compounds. XXIII. Organomercuric Quinolin-8-olates
Publisher: CSIRO Publishing
Date: 1978
DOI: 10.1071/CH9780527
Abstract: The complexes RHg(ox) (R = C6F5, p-HC6F4, or p-MeOC6F4 ox = quinolin-8- olate) have been prepared by reaction of thallous quinofin-8-olate with the appropriate organomercuric chlorides whilst PhHg(ox or meox), MeHg(ox),H2O, and MeHg(meox) (meox = 2-methylquinolin-8-olate) have been obtained from phenyl- or methyl-mercuric hydroxide and quinolin-8-ol or 2-methyl-quinolin-8-ol. Although MeHg(ox),H2O was readily dehydrated, the water could not be displaced by ligands (e.g. Ph3PO, Me2SO). Chelation of the quinolin-8-olate ligands (rather than unidentate O- bonding) was established for all complexes by ultraviolet/visible spectroscopy. Molecular weight data indicated that all complexes except MeHg(ox) and MeHg(ox),H2O are partly associated in benzene, chloroform and/or carbon tetrachloride [K(2 monomer ↔ dimer) in the range 1-40 mol-1 dm3] this suggests an associated structure in the solid state. Some supporting evidence for associated structures was obtained by mass spectrometry. The structural conclusions are discussed in the light of crystal structures of PhHg(ox) and PhHg(meox) carried out in a concurrent investigation.
Formation of a cyclooctatetraenylsamarium(iii ) inverse sandwich that ring-opens tetrahydrofuran
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2DT04164B
Abstract: Reductive trapping of the cyclooctatetraenyl dianion by treatment of [Sm(DippForm) 2 (thf) 2 ] {DippFormH = N , N ′-bis(2,6-diisopropylphenyl)formamidine} with cyclooctatetraene in toluene yields an inverse sandwich dinuclear complex [Sm 2 (DippForm) 4 (COT)].
Synthesis and Characterization of the Zinc Amides: [EtZnL]2 and [ZnL2] (L = N,N‐dimethyl(N′‐trimethylsilyl)ethane‐1,2‐diaminate)
Publisher: Wiley
Date: 02-01-2007
Organoamidometallics—IV. Syntheses of N,N′-bis(polyfluorophenyl)ethane-1,2-diaminato(2−)platinum(II) complexes with two different fluorocarbon groups
Publisher: Elsevier BV
Date: 1991
Structural diversity of lanthanoid salicylate hydrates
Publisher: Elsevier BV
Date: 12-2016
Cerium acetylacetonates - new aspects, including the lamellar clathrate [Ce(acac)4]10H2O
Publisher: Elsevier BV
Date: 08-2003
Adventitiously Obtained Rare-Earth Peroxide Complexes and Their Structural Characterisation
Publisher: CSIRO Publishing
Date: 2014
DOI: 10.1071/CH14410
Abstract: The structures of three adventitiously obtained peroxolanthanoid complexes have been determined, namely, [Yb2(Cp)4(μ-O)2/3(μ-O2)1/3(thf)2] (1) (Cp = cyclopentadienyl thf = tetrahydrofuran), which has disorder between the bridging oxide and peroxide, [Nd2(o-PhPhForm)4(thf)4(μ-O2)] (2) (o-PhPhForm = N,N′-bis(2-phenylphenyl)formamidinate), and [Eu4(FForm)6(μ-OH)2(μ3-O2)2(μ-diglyme)2]·2diglyme (3) (FForm = N,N′-bis(2-fluorophenyl)formamidinate, diglyme = bis(2-methoxyethyl) ether). In the first two complexes, the peroxide bridges side-on between metals, whereas in the last complex, each peroxide bridges three metals through both oxygen atoms. The first complex was a single crystal amongst a bulk s le of [Yb(Cp)2(pzPh)(thf)] (pzPh = 2-(1′-pyrazolyl)phenyl), prepared by oxidation of dicyclopentadienylytterbium(ii) by bis(2-(1′-pyrazolyl)phenyl)mercury, the structure of which was also determined and showed distorted square planar stereochemistry for mercury.
Physical trends and structural features in organic salts of the thiocyanate anion
Publisher: Royal Society of Chemistry (RSC)
Date: 29-10-2002
DOI: 10.1039/B208372H
Synthesis of fluoro(aryloxo)alkaline earth metal cages by C–F bond activation
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0DT00122H
Abstract: Treatment of Ca or Sr metal with Hg(C(6)F(5))(2) and 2,4,6-trimethylphenol (HOmes) in 1,2-dimethoxyethane (dme) at room temperature resulted in C-F bond activation, giving rise to the unique fluoro(aryloxo)alkaline earth cages [Ca(5)(mu(4)-F)(mu(3)-F)(4)(mu-Omes)(4)(Omes)(dme)(4)] 1 and [Sr(10)(mu(4)-F)(4)(mu(3)-F)(4)(mu-Omes)(12)(dme)(4)] 2, which can be viewed as arrested fluorite structures.
The synthesis of alkylmanganese(III) complexes. Crystal structure of MnMe(2-Me2NCH2C6H4)2
Publisher: Elsevier BV
Date: 02-1992
Trispentafluorophenylbismuth — A correction
Publisher: Elsevier BV
Date: 10-1972
Modifying the properties of platinum(IV) complexes in order to increase biological effectiveness
Publisher: Elsevier BV
Date: 10-1999
DOI: 10.1016/S0162-0134(99)00133-6
Abstract: The preparation of a series of novel Pt(IV) complexes containing the anionic polyfluoroaryl ligands, 2,3,5,6-tetrafluorophenyl (p-HC6F4), 2,3,5,6-tetrafluoro-4-methoxyphenyl (p-MeOC6F4) and pentafluorophenyl (C6F5) are described. The crystal structure of a representative complex, [Pt(p-MeOC6F4)2(O2CEt)2(en)] (en = ethane-1,2-diamine) was determined and confirms the trans arrangement of the carboxylato ligands. Reduction potentials of the series of complexes reveal that replacement of equatorial chloro ligands by polyfluoroaryl ligands makes reduction substantially more difficult. They also confirm previously reported trends in that complexes having axial carboxylato ligands are more readily reduced than those having axial hydroxo ligands. Reduction potentials and in vitro activities showed no obvious correlations. Moderate to high activity was observed for many complexes in the series, including some of those that were very difficult to reduce.
Decarboxylation syntheses of transition metal organometallics. III polyfluorophenylplatinum(II) complexes with nitrogen donor ligands
Publisher: Springer Science and Business Media LLC
Date: 04-1982
DOI: 10.1007/BF00618192
Tris(triazenido)thalium(III)compounds
Publisher: Elsevier BV
Date: 1979
Two Dieneplatinum Synthetic Reagents, Pt(C6H2F3-2,4,6)2(cod) and Pt(C6HF4-2,3,4,5)2(cod)
Publisher: Wiley
Date: 2002
DOI: 10.1002/1521-3749(200201)628:1<167::AID-ZAAC167>3.0.CO;2-0
Organothallium compounds XII NMR spectra of some polyfluorophenylthallium (III) compounds
Publisher: Elsevier BV
Date: 1978
Enantiopure dimagnesium(i) and magnesium(ii) hydride complexes incorporating chiral amidinate or β-diketiminate ligands
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0CC07947B
Abstract: The first ex les of enantiopure, dinuclear magnesium( i ) and magnesium( ii ) hydride complexes have been kinetically stabilised using bulky chiral β-diketiminate and amidinate ligands (see picture).
C–H Bond Activation and Isoprene Polymerization by Rare-Earth-Metal Tetramethylaluminate Complexes Bearing Formamidinato N-Ancillary Ligands
Publisher: American Chemical Society (ACS)
Date: 09-01-2013
DOI: 10.1021/OM301010M
Six coordinate complexes of diorganothallium(III) compounds
Publisher: Elsevier BV
Date: 05-1969
Organolanthanoids.X. Syntheses of Cyclopentadienyllanthanoids by Transmetalation Reactions in Pyridine, Acetonitrile and Ethers
Publisher: CSIRO Publishing
Date: 1987
DOI: 10.1071/CH9870895
Abstract: The complexes, (C5H5)3M( py ) (M = Nd, Sm, Eu or Yb ), (C5H5)2Eu( py ), and (C5H5)2Yb( py )2 have been prepared from the appropriate lanthanoid elements and thallous cyclopentadienide in pyridine, and (C5H5)3M( NCMe ) (M = Nd , Sm or Yb ) and (C5H5)2Yb( NCMe ) from similar reactions in acetonitrile. Ligand exchange or addition has also been used to give (C5H5)3Sm( py ), (C5H5)2Yb( py )2 and (C5H5)2Yb( NCMe ). Ytterbium metal reduces (C5H5)3Yb( py ) in pyridine to (C5H5)2Yb( py )2, which is oxidized back to (C5H5)3Yb( py ) by TI(C5H5). Europium with (C5H5)2Hg in tetrahydrofuran yields (C5H5)3Eu( thf ), and (C5H5)2Eu is not isolated by using an excess of metal. Oxidation of (C5H5)2Eu to (C5H5)3Eu is effected by (C5H5)2Hg in tetrahydrofuran but not by T1(C5H5) in 1,2-dimethoxyethane. Europium and ytterbium react with bis(pentafluoropheny1)mercury and cyclopentadiene in pyridine to give (C5H5)3M( py ) (M = Eu or Yb ).
Organolanthanoid-halide synthons—a new general route to monofunctionalized lanthanoid(ii) compounds?
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0CC01317J
Abstract: New Eu(II) and Yb(II) complexes [Ln(Ph(2)pz)I(thf)(4)] were synthesized from the corresponding metals and 3,5-diphenylpyrazole (HPh(2)pz) using iodobenzene as oxidizing agent. In the absence of the pyrazole, the charge separated Yb(II)/Yb(III) complex [{Yb(dme)(4)}{YbPh(4)(dme)}(2)] has been isolated.
Novel Coordination Complexes in the Bismuth(III)/Oxinate System
Publisher: Wiley
Date: 26-06-2006
Abstract: Single crystal structural characterizations are reported for a pair of bismuth(III)/oxinate ('ox') complexes, formulated as [Bi(ox) 3 (OH 2 )] 2 and [BiPh(ox) 2 ( O ‐dmso)] 2 respectively. In the former, analytically significant, species the Bi(ox) 3 coordination sphere is augmented by dimerization by way of bridging interactions through two of the ox oxygen donor atoms and a residue modelled as a coordinated water molecule oxygen atom. In the dmso complex, a novel pentagonal pyramidal coordination environment (Ph at the apex) is described, presumably consequent on the effect of close η 6 ‐interactions of the bismuth with the carbocyclic ring of one of the ox ligands of an adjacent, inversion‐related molecule.
Mixed-ligand ytterbium(iii) complexes incorporating one or two bidentate (N,O) amide ligands
Publisher: Royal Society of Chemistry (RSC)
Date: 2003
DOI: 10.1039/B303724J
Organothallium compounds X the formation of polyfluorophenylthallium compounds by desulphination reactions
Publisher: Elsevier BV
Date: 11-1975
Direct Reactions of Iodine‐Activated Rare‐Earth Metals with Phenols of Varying Steric Bulk
Publisher: Wiley
Date: 12-12-2013
Abstract: Sonication of rare‐earth metals activated by iodine with 2,6‐di‐ tert ‐butyl‐4‐methylphenol (HOdbmp), 2,6‐diphenylphenol (HOdpp) and mesitol (HOmes) in acetonitrile or tetrahydrofuran (thf) yielded [La(Odbmp) 3 (NCMe) 2 ], [Eu(Odbmp) 2 (thf) 3 ], [Ln(Odpp) 3 (thf) 2 ] (Ln = La, Nd), [Eu(Odpp) 2 (dme) 2 ] (after workup with 1,2‐dimethoxyethane), [Ln 2 (Omes) 6 (thf) 4 ] (Ln = La, Nd), [Y(Omes) 3 (thf) 3 ] and [Eu 3 (Omes) 6 (thf) 6 ] in reactions controlled both by the bulk of the phenol and of the metal. It was noteworthy that Eu II complexes were obtained under the conditions used. The method offers a general, environmentally friendly, metal‐based route to rare‐earth phenolates with prospects for wide application. Some comparison reactions of Ln metals with Hg(C 6 F 5 ) 2 and the phenols were also carried out and the additional complex [Eu(Odpp) 3 (dme)] was isolated. Structures of the new low‐coordinate complexes [La(Odbmp) 3 (NCMe) 2 ] · 2MeCN, [Eu(Odpp) 2 (dme) 2 ] and [Eu(Odpp) 3 (dme)], and a new polymorph of [Eu(Odbmp) 2 (thf) 3 ] · thf, were determined.
Linear Trinuclear Copper(II) Complexes Derived from the Nucleophilic Addition Products of Dicyanonitrosomethanide [C(CN)2(NO)]–: Syntheses, Structures, and Magnetic Properties
Publisher: CSIRO Publishing
Date: 2012
DOI: 10.1071/CH12100
Abstract: Two novel trinuclear CuII complexes have been synthesised from the nucleophilic addition derivatives of the small cyano anion, dicyanonitrosomethanide (dcnm). The reaction of CuII with the water adduct ligand, carbamoylcyanonitrosomethanide (ccnm) and teaH3 (triethanolamine) in a basic MeOH/MeCN solution results in the formation of [Cu3(acnm)2(teaH2)2]·2MeOH (1) (acnm = amidocarbonyl(cyano)nitrosomethanide and teaH2– = singly deprotonated triethanolamine). The reaction of CuII with dicyanonitrosomethanide (dcnm) and m-xylenediamine in a basic MeOH/MeCN solution results in the formation of [Cu3(cimm)2(a3acnm)2]·6MeCN (2) (cimm = cyano(imido(methoxy)methyl)nitrosomethanide and a3acnm = {amino(3-aminomethylphenyl)methylimino}methyl(cyanonitrosomethanide)). Both complexes display linear trinuclear CuII metallic cores. Solid state DC magnetic susceptibility studies were performed on 1 and 2. Compound 1 revealed very strong antiferromagnetic interactions between central and terminal Cu atoms, while compound 2 displayed ferromagnetic interactions because of the orthogonal relationship of the terminal and the central ‘magnetic’ orbitals, which contrasts with these orbitals being coplanar in 1 thus providing strong superexchange pathways involving Cu-N-O-Cu moieties.
Organolanthanoids XIX. The X-ray crystal structures of di [μ-(acetato-O,O:O′)bis(diphenylphosphino-η5-cyclopentadienyl)ytterbium(III)] and di[μ-(acetato-O,O:O′)bis(η5-cyclopentadienyl)ytterbium(III)]
Publisher: Elsevier BV
Date: 10-1995
Selection of organometallics for MOCVD of Hg1−xCdxTe and doped semiconductors
Publisher: Elsevier BV
Date: 1990
Reductive Trapping of [(OC)5W–W(CO)5]2− in a Mixed‐Valent SmII/III Calix[4]pyrrolide Sandwich
Publisher: Wiley
Date: 14-06-2017
Ruthenium carbonyl complexes. I. Synthesis of [Ru(CO)2(bidentate)2]2+ complexes
Publisher: CSIRO Publishing
Date: 1982
DOI: 10.1071/CH9822445
Abstract: The complexes RU(CO)2Cl2L [L = 1,l0-phenanthroline (phen) or 2,2'-bipyridyl (bpy)] react with silver carboxylates to yield Ru(CO)2(OCOR)2L derivatives (R = Me or CF3). Reactions of Ru(CO)2(OAc)2L and Ru(CO)2(OAc)2(phen) with trifluoroacetic and trifluoromethanesulfonic acid give Ru(CO)2(OCOCF3)2L and Ru(CO)2(OSO2CF3)2(phen) respectively. In acetonitrile, Ru(CO)2(OAC)2L complexes react with trifluoromethanesulfonic acid to give [Ru(CO)2(MeCN)2L] (O3SCF3)2. The complexes [RU(CO)2L2]2+, [Ru(CO)2(phen)(bpy)]2+, and [Ru(C02(phen)(tmp)]2+ (tmp = 3,4,7,8-tetramethyl-1,l0-phenanthroline) have been prepared by reaction of [Ru(CO)2- (MeCN)2L]2+ and/or Ru(CO)2(OSO2CF3)2 phen with an excess of the appropriate bidentate ligand. A similar series of reactions has yielded Ru(C0)2(OAc)2(py)2, [Ru(CO)2(MeCN)2(py)2] (O3SCF3)2, and [RU(CO)2(py)2L]2+ from Ru(CO)2Cl2(py)2. Stereochemical assignments have been made for all complexes.
Preparation and X-Ray Structure of [YbIII(η5-C5H5)2(OPPh3)(OPPh2C5H4)]—a Complex With Oxygen Rather Than Cyclopentadienide Coordination of a Novel Ambidentate Ligand
Publisher: CSIRO Publishing
Date: 1992
DOI: 10.1071/CH9921939
Abstract: No Abstract Available.
Efficient synthetic route to heterobimetallic trinuclear complexes [Ln-Mn-Ln] and their single molecule magnetic properties.
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2DT02616C
Abstract: A series of mononuclear lanthanoidate complexes isolated as [Bu
The formation of polyfluorophenylplatinum(II) compounds by sulphur dioxide elimination reactions
Publisher: Elsevier BV
Date: 09-1985
Synthesis and Structures of Two Thiocyanato-Lanthanoid Cages
Publisher: Springer Science and Business Media LLC
Date: 04-05-2010
The reactions of metal complexes with alkyl halides—II The reactions of halo(triphenylphosphine)-cadmium(II) complexes
Publisher: Elsevier BV
Date: 12-1962
Regiospecific replacement of fluorine by hydrogen in an aromatic ring induced by a rare earth organometallic
Publisher: Elsevier BV
Date: 02-1994
Insertion of tellurium into an alkylpentacarbonylmanganese complex and a convenient new route to manganese telluride
Publisher: Royal Society of Chemistry (RSC)
Date: 1990
DOI: 10.1039/C39900001293
Low viscosity ionic liquids based on organic salts of the dicyanamide anion
Publisher: Royal Society of Chemistry (RSC)
Date: 2001
DOI: 10.1039/B103064G
X‐ray Crystal Structure Characterization of Two Mononuclear Low Coordinate Lanthanoid Aryloxides, [La(Odpp)3(dig)]·0.5dig and [Nd(Odpp)3(py)2]·2py, (HOdpp = 2,6‐diphen
Publisher: Wiley
Date: 23-08-2006
Abstract: Structures of the new complexes [La(Odpp) 3 (dig)] · 0.5dig (Odpp = 2,6‐diphenylphenolate dig = bis(2‐methoxyethyl) ether – diglyme) and [Nd(Odpp) 3 (py) 2 ] · 2py (py = pyridine), obtained by crystallization of the corresponding [Ln(Odpp) 3 (thf) 2 ] complex from diglyme or pyridine contain six‐coordinate and five‐coordinate lanthanoid atoms respectively. In the former, two meridional sets of donor atoms, (O 3 (dig) and O 3 (Odpp)) are near normal to each other and in a highly distorted octahedral stereochemistry, whereas the latter is trigonal bipyramidal with an oxygen and a nitrogen atom apical and a pronounced lengthening of the axial Nd‐N bond.
A spectroscopic investigation into the binding of novel platinum(IV) and platium(II) anticancer drugs with DNA
Publisher: Elsevier BV
Date: 09-2017
Element interchange reactions of bromobis(pentafluorophenyl)thallium(III)
Publisher: Elsevier BV
Date: 05-1969
Bulky Formamidinate-Supported Lanthanoid Halides and Alkyls, Including a Rare Terminal La–Me Species
Publisher: American Chemical Society (ACS)
Date: 24-12-2012
DOI: 10.1021/OM301048B
When Metathesis Reactions Go Wrong: Novel Structural Consequences
Publisher: Wiley
Date: 18-11-2008
Alkaline Earth Metal Organoamide Complexes Displaying Close Ae–F(C) (Ae = Ca, Mg) Interactions
Publisher: CSIRO Publishing
Date: 2013
DOI: 10.1071/CH13228
Abstract: Protolysis of [Ca{N(SiMe3)2(thf)2] (thf = tetrahydrofuran) with the N,N-dialkyl-N′-2,3,5,6-tetrafluorophenylethane-1,2-diamines, p-HC6F4NH(CH2)2NR2 (LRH R = Me or Et), yields [Ca(p-HC6F4N(CH2)2NR2)2(thf)2], whilst protolysis of di-n-butylmagnesium by the same amines yields [Mg(p-HC6F4N(CH2)2NR2)2] complexes. X-Ray crystal structures show that the calcium derivatives contain eight-coordinate calcium atoms, with tridentate (N,N′,o-F) coordination of the organoamide ligands and cisoid thf donors. It is noteworthy that the Ca–F(C) bond lengths are shorter than the Ca–NR2 bond lengths. By contrast, magnesium forms centrosymmetric, six-coordinate, homoleptic complexes, in which the Mg–NR2 bond lengths are shorter than the Mg–F(C) bond lengths. 19F{1H} NMR spectra of the R = Me complexes support retention of Ae–F(C) linkages in solution at low temperatures. Heating the complexes for a prolonged period in C6D6 at 80°C showed no evidence of C–F activation reactions.
Nucleophilic Aromatic Substitution of Bis(pentafluorophenyl)mercury with Various Bulky Nucleophiles and the Structures of [Hg(C6F4X-4)2] (X=cyclo-C5H10N, OCH(CH3)2, OC(CH3)3)
Publisher: CSIRO Publishing
Date: 2013
DOI: 10.1071/CH13227
Abstract: Reactions of bis(pentafluorophenyl)mercury with piperidine, sodium iso-propoxide or sodium tert-butoxide have yielded the corresponding 4-substituted tetrafluorophenylmercurials, [Hg(C6F4X-4)2] (X = cyclo-C5H10N (1), OCH(CH3)2 (2), OC(CH3)3 (3)), in reasonable yields but the bulkier nucleophiles, cis-2,6-dimethylpiperidine and 2,6-di-iso-propylphenolate (from sodium 2,6-di-iso-propylphenolate) decomposed the mercurial into pentafluorobenzene. Treatment of bis(pentafluorophenyl)mercury with another bulky nucleophile, 2,6-diphenylphenolate (from sodium 2,6-diphenylphenolate), in methanol, resulted in the unexpected formation of [Hg(C6F4(OMe)-4)2] (4). The structures of all the mercurials have linear C–Hg–C stereochemistry with two coplanar aryl rings. Amongst a complex series of supramolecular interactions, Hg⋯O bonding is observed for the alkoxy substituted mercurials but there are no Hg⋯N interactions in the structure of bis(2,3,5,6-tetrafluoro-4-piperidinophenyl)mercury.
Octanol/water partition coefficients as a model system for assessing antidotes for methylmercury(ii) poisoning, and for studying mercurials with medicinal applications
Publisher: Elsevier BV
Date: 09-1984
DOI: 10.1016/0162-0134(84)85064-3
Abstract: 1-Octanol/water partition coefficients, [HgII]octanol/[HgII]water, provide a simple but limited model system for aspects of the biological behavior of methylmercury(II) and commonly used organomercury(II) medicinal compounds. In an octanol/water system some widely studied antidotes for mercury poisoning at least partly displace the biological thiols L-cysteine and glutathione from binding to MeHgII at pH 6.9. Addition of the antidote meso-dimercaptosuccinic acid to MeHgII in the presence of glutathione results in formation of metallic mercury. For RHgII derivatives of L-cysteine and glutathione, octanol/water partition coefficients follow the order Ph greater than Et greater than Me. An exceptionally high value for diphenylmercury, compared with PhHgII derivatives of L-cysteine and glutathione, is consistent with reported results of the distribution of mercury compounds in rats. Ethylmercury(II) is partly displaced from thimerosal by L-cysteine and glutathione in the octanol/water system, indicating that the active form of thimerosal in vivo may involve binding of EtHgII to biological ligands.
Crystal Structure of a CeIII/FeIII Heterobimetallic Complex
Publisher: Wiley
Date: 08-2003
Synthesis and bromodemercuration of some permercurated arenes
Publisher: CSIRO Publishing
Date: 1976
DOI: 10.1071/CH9760627
Abstract: Pentabromonitrobenzene, pentabromobenzoic acid, pentabromobenzamide, pentabromoacetanilide, barium pentabromobenzenesulphonate, 1,2,4,5 - tetrabromo -3-chloro-6-(trifluoromethyl)benzene, 2,3,5,6-tetrabromo-4-methoxytoluene 2,3,5,6-tetrabromo-4-methoxybenzamide, methyl 2,3,5,6-tetra- bromo-4-methoxybenzoate, and 1,2,5-tribromo-3,4-dichloro-6-fluorobenzene have been synthesized in good yield by bromodemercuration of the corresponding fully mercurated (permercurated) arenes, e.g. C6(HgO2CCF3)5NO2, which were prepared by reaction of an excess of molten mercuric tri- fluoroacetate with suitable arenes at c. 180-245�. Permercuration of p-methoxybenzoic acid was accompanied by complete decarboxylation giving, after bromodemercuration, pentabromo(methoxy)- benzene, which was also obtained in low yield from preparations of methyl 2,3,5,6-tetrabromo-4- methoxybenzoate and 2,3,5,6-tetrabromo-4-methoxybenzamide. Conditions have been devised for conversion of phenylmercuric chloride into either a pentamercurated or a hexamercurated benzene derivative, and hence into pentabromo-or hexabromobenzene. The results establish permercuration/bromodemercuration as a simple and versatile route to polybromobenzene.
Synthesis and Structure of ‘mer’‐Trichlorotetrakis(pyridine)ytterbium(III) Hemipyridine Solvate
Publisher: Wiley
Date: 23-08-2006
Abstract: The title compound [YbCl 3 (py) 4 ]·0.5py has been grown as single crystals by the treatment of ytterbium chunks with hexachloroethane in pyridine and characterized by a single crystal X‐ray study. It is isomorphous with the previous [LnCl 3 (py) 4 ]·0.5py array defined for Ln = La, Eu, Er, extending the ‘domain of existence’ of that form to Ln = Yb, an unexpected result given that the Ln = Y adduct with similar seven‐coordinate, pentagonal bipyramidal coordination environment, is of an unsolvated form.
Experimental and Theoretical Investigations of the Effect of Deprotonation on Electronic Spectra and Reversible Potentials of Photovoltaic Sensitizers: Deprotonation of cis-L2RuX
Publisher:
American Chemical Society (ACS)
Date:
21-12-1999
DOI:
10.1021/JA992402G
Publisher: American Chemical Society (ACS)
Date: 21-12-1999
DOI: 10.1021/JA992402G
Low-coordinate rare-earth complexes of the asymmetric 2,4-di-tert-butylphenolate ligand prepared by redox transmetallation/protolysis reactions, and their reactivity towards ring-opening polymerisatio
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0DT00023J
Abstract: New trivalent lanthanoid aryloxide complexes have been prepared by redox transmetallation rotolysis (rtp) reactions using 2,4-di-tert-butylphenol (dbpH). Mononuclear octahedral complexes from tetrahydrofuran (thf) were of the type [Ln(dbp)(3)(thf)(3)] (Ln = La (1), Pr (2), Nd (3), Gd (4), Er (5)). The lanthanoid contraction results in the rather subtle change in stereochemistry from meridional (La, Pr, Nd, Gd) to facial (Er). An analogous reaction with neodymium in dimethoxyethane (dme), resulted in the isolation of the seven coordinate [Nd(dbp)(3)(dme)(2)] (6), and this is comparable with the thf complexes in terms of steric crowding. Dinuclear complexes of the type [Ln(2)(dbp)(6)(thf)(2)], (Ln = Nd (7), Er (8)) were obtained when 1 and 5 were recrystallised from toluene. These dimeric complexes contain two bridging and four terminal phenolates, as well as a single coordinated molecule of thf at each metal. A similar structural motif was observed for the products when the reaction was performed in diethyl ether, and in the absence of a solvent, yielding [Nd(2)(dbp)(6)(Et(2)O)(2)] (9) and [Nd(2)(dbp)(6)(dbpH)(2)] (10) respectively. Complexes 3 and 4 alone were efficient but poorly-controlled initiators for the ROP of rac-lactide, but with an excess of BnOH as a co-initiator they showed features consistent with immortal polymerisation. Use of BnNH(2) led to well-controlled, amine-initiated immortal ROP of rac-lactide, only the second report of this type of process for a group 3 or lanthanoid system.
Organomercury compounds. XVIII. Thermal decomposition reactions of mercuric arenesulphonate pyridinates
Publisher: CSIRO Publishing
Date: 1973
DOI: 10.1071/CH9731893
Abstract: The mercuric arenesulphonate pyridinates, Hg(O3SR)2,(py)2 (R = C6X5, p- HC6X4, o-HC6X4, or m-HC6Cl4 X = Cl or F) and Hg(O3S-m-HC6F4)2,(py)3, have been prepared by treatment of the appropriate mercuric arenesulphonate dihydrates with pyridine. Thermal decomposition of the compounds Hg(O3SR)2,(py)2 (R = C6X5, p-HC6X4, or m-HC6Cl4) and Hg(O3S-m-HC6F4)2,(py)3 at c. 120-240� under vacuum gave the corresponding diarylmercurials (yields: 45-90%) and the complex (py),SO3 in all cases, together with (- m-HgC6F4SO3-)n, and low yields of polyfluorobenzenes and/or polyfluorobenzenesulphonic acids. Similar decomposition of the compounds Hg(O3S-o-HC6X4)2,(py)2 gave (-o-HgC6X4SO3-)n, (py),SO3, o- HC6X4SO3H, and o-H2C6X4, and there was some evidence for formation of a trace of o-(o-HC6Cl4- SO3Hg)C6Cl4SO3HgO3S-o-HC6Cl4. The derivatives (- HgC6X4SO3-)n, were identified by established degradation procedures.
The Infrared Spectra of Quaternary 'Onium Cations of Group VB Elements. I. Vibrational Assignments for Some Tetramethylphosphonium Salts
Publisher: CSIRO Publishing
Date: 1962
DOI: 10.1071/CH9620555
Reinvestigation of Reactions of HgPh2 with Eu and Yb Metal and the Synthesis of a Europium(II) Bis(tetraphenylborate)
Publisher: MDPI AG
Date: 03-11-2022
DOI: 10.3390/MOLECULES27217547
Abstract: Europium bis(tetraphenylborate) [Eu(thf)7][BPh4]2⋅thf containing a fully solvated [Eu(thf)7]2+ cation, was synthesized by protolysis of “EuPh2” (from Eu and HgPh2) with Et3NHBPh4, and the structure was determined by single-crystal X-ray diffraction. Efforts to characterize the putative “Ph2Ln” (Ln = Eu, Yb) reagents led to the synthesis of a mixed-valence complex, [(thf)3YbII(μ-Ph)3YbIII(Ph)2(thf)]⋅2thf, resulting from the reaction of Yb metal with HgPh2 at a low temperature. This mixed-valence YbII/YbIII compound was studied by 171Yb-NMR spectroscopy and single-crystal X-ray diffraction, and the oxidation states of the Yb atoms were assigned.
Synthesis, structure, and corrosion inhibiting properties of REIII 3-thiophenecarboxylate complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2NJ03556A
Abstract: Two series of Rare Earth (RE) 3-thiophencarboxylate (3TPC) complexes have been synthesized by reactions between a RE salt and Na(3TPC). Based on weight loss measurements and potentiodynamic polarization measurements, the compounds show good corrosion inhibitory properties and act mainly as anodic inhibitors.
Stabilization of Aryl–Calcium, –Strontium, and –Barium Compounds by Designed Steric and π‐Bonding Encapsulation
Publisher: Wiley
Date: 08-09-2005
Synthesis, spectroscopy, and theoretical studies of platinum(ii) phosphate complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2002
DOI: 10.1039/B111460N
2,6-Diphenylphenolates of calcium, strontium and barium exhibiting π-phenyl encapsulation of the partially naked cations
Publisher: Elsevier BV
Date: 08-2000
Organomercury Compounds .XXVIII. The Synthesis and 199Hg N.M.R-Spectra of Some Unsymmetrically Dimercurated Arenes
Publisher: CSIRO Publishing
Date: 1986
DOI: 10.1071/CH9860953
Abstract: Mercuration of 1-methoxy-2-nitrobenzene (1) with mercuric trifluoroacetate (mole ratio 1 : 1) in trifluoroacetic acid yields 1- methoxy-2-nitro-4-(trifluoroacetatomercurio)benzene (2). With a 1 : 2 mole ratio, (2) and 1-methoxy-2-nitro-4,6- bis(trifluoroacetatomercurio)benzene (3) are obtained, and, with a 1:4 ratio, (3) and a little 1-methoxy-2-nitro-3,4- bis(trifluoroacetatomercurio)benzene (4). are obtained. 2-Nitrophenol (5) with mercuric trifluoroacetate (mole ratio 1 : 2) gives 2-nitro- 4,6-bis(trifluoroacetatomercurio)phenol (6), and vanillin (7) yields 5,6-bis(trifluoroacetatomercurio)vanillin (8). Compound (8) has been converted into 5,6-di(chloromercurio)- and 5,6- di(bromomercurio)vanillin [(9) and (10)]. 199Hg,199Hg spin-spin coupling constants have been determined s 6500-8200 Hz for 3JHg,Hg of (8)- (10), 2100-2200 Hz for 4JHg,Hg of (3) and (6), and 858 Hz for 5JHg,Hg of 4- methoxy-2,5-bis(trifluoroacetatomercurio)benzoic acid (11).
Cerium(III/IV) Formamidinate Chemistry, and a Stable Cerium(IV) Diolate
Publisher: Wiley
Date: 18-03-2014
Abstract: Four new cerium(III) formamidinate complexes comprising [Ce(p-TolForm)3 ], [Ce(DFForm)3 (thf)2 ], [Ce(DFForm)3 ], and [Ce(EtForm)3 ] were synthesized by protonolysis reactions using [Ce{N(SiMe3 )2 }3 ] and formamidines of varying functionality, namely N,N'-bis(4-methylphenyl)formamidine (p-TolFormH), N,N'-bis(2,6-difluorophenyl)formamidine (DFFormH), and the sterically more demanding N,N'-bis(2,6-diethylphenyl)formamidine (EtFormH). The bimetallic cerium lithium complex [LiCe(DFForm)4 ] was synthesized by treating a mixture of [Ce{N(SiHMe2 )2 }3 (thf)2 ] and [Li{N(SiHMe2 )2 }] with four equivalents of DFFormH in toluene. Oxidation of the trivalent cerium(III) formamidinate complexes by trityl chloride (Ph3 CCl) caused dramatic color changes, although the cerium(IV) species appeared transient and reformed cerium(III) complexes and N'-trityl-N,N'-diarylformamidines shortly after oxidation. The first structurally characterized homoleptic cerium(IV) formamidinate complex [Ce(p-TolForm)4 ] was obtained through a protonolysis reaction between [Ce{N(SiHMe2 )2 }4 ] and four equivalents of p-TolFormH. [Ce{N(SiHMe2 )2 }4 ] was also treated with DFFormH and EtFormH, but the resulting cerium(IV) complexes decomposed before isolation was possible. The new cerium(IV) silylamide complex [Ce{N(SiMe3 )2 }3 (bda)0.5 ]2 (bda=1,4-benzenediolato) was synthesized by treatment of [Ce{N(SiMe3 )2 }3 ] with half an equivalent of 1,4-benzoquinone, and showed remarkable resistance towards protonolysis or reduction.
Europium is Different: Solvent and Ligand Effects on Oxidation State Outcomes and C‐F Activation in Reactions Between Europium Metal and Pentafluorophenylsilver
Publisher: Wiley
Date: 08-12-2021
Abstract: Unique outcomes have emerged from the redox transmetallation/ protolysis (RTP) reactions of europium metal with [Ag(C 6 F 5 )(py)] (py=pyridine) and pyrazoles (RR′pzH). In pyridine, a solvent not normally used for RTP reactions, the products were mainly Eu II complexes, [Eu(RR′pz) 2 (py) 4 ] (RR′pz=3,5‐diphenylpyrazolate (Ph 2 pz) 1 3‐(2‐thienyl)‐5‐trifluoromethylpyrazolate (ttfpz) 2 3‐methyl‐5‐phenylpyrazolate (PhMepz) 3 ). However, use of 3,5‐di‐ tert ‐butylpyrazole ( t Bu 2 pzH) gave trivalent [Eu( t Bu 2 pz) 3 (py) 2 ] 4 , whereas the bulkier N,N′‐bis(2,6‐difluorophenyl)formamidine (DFFormH) gave alent [Eu(DFForm) 2 (py) 3 ] 5 . In tetrahydrofuran (thf), the usual solvent for RTP reactions, C−F activation was observed for the first time with [Ag(C 6 F 5 )(py)] in such reactions. Thus trivalent [{Eu 2 (Ph 2 pz) 4 (py) 4 (thf) 2 (μ‐F) 2 }{Eu 2 (Ph 2 pz) 4 (py) 2 (thf) 4 (μ‐F) 2 }] ( 6 ), [Eu 2 (ttfpz) 4 (py) 2 (dme) 2 (μ‐F) 2 ] ( 7 ), [Eu 2 ( t Bu 2 pz) 4 (dme) 2 (μ‐F) 2 ] ( 8 ) were obtained from the appropriate pyrazoles, the last two after crystallization from 1,2‐dimethoxyethane (dme). Surprisingly 3,5‐dimethylpyrazole (Me 2 pzH) gave the alent cage [Eu 6 (Me 2 pz) 10 (thf) 6 (μ‐F) 2 ] ( 9 ). This has a compact ovoid core held together by bridging fluoride, thf, and pyrazolate ligands, the last including the rare μ 4 ‐1η 5 ( N 2 C 3 ): 2η 2 ( N,N′ ): 3κ( N ): 4κ( N′ ) pyrazolate binding mode. With the bulky N,N′‐bis(2,6‐diisopropylphenyl)formamidine (DippFormH), which often favours C−F activation in RTP reactions, neither oxidation to Eu III nor C−F activation was observed and [Eu(DippForm) 2 (thf) 2 ] ( 10 ) was isolated. By contrast, Eu reacted with Bi(C 6 F 5 ) 3 and Ph 2 pzH or t Bu 2 pzH in thf without C−F activation, to give [Eu(Ph 2 pz) 2 (thf) 4 ] ( 11 ) and [Eu( t Bu 2 pz) 3 (thf) 2 ] ( 12 ) respectively, the oxidation state outcomes corresponding to that for use of [Ag(C 6 F 5 )(py)] in pyridine.
Studies of the binding of a series of platinum(IV) complexes to plasma proteins
Publisher: Elsevier BV
Date: 02-2002
DOI: 10.1016/S0162-0134(01)00360-9
Abstract: The platinum(IV) complexes: [PtCl(4)(en)], cis,trans-[PtCl(2)(OAc)(2)(en)], cis,trans-[PtCl(2)(OH)(2)(en)] and trans-[Pt(OH)(2)(ethmal)(en)], encompassing a range of reduction potentials and their platinum(II) analogue [PtCl(2)(en)], have been assayed for their protein binding ability in the presence of albumin, albumin and L-cysteine and RPMI 1640 tissue culture medium supplemented with foetal calf serum (RPMI/FCS). cis,trans-[PtCl(4)(en)] exhibited significant protein binding in all three experiments, in a similar fashion to the platinum(II) complex, presumably as a consequence of its rapid reduction. The remaining three platinum(IV) complexes displayed little if any protein binding, with the greatest amount of binding observed in the RPMI/FCS experiment. The extent of binding in the RPMI/FCS correlated with the reduction potentials of the complexes, with the most readily reduced species binding to the greatest extent.
Bulky Cations and Four different Polyiodide Anions in [Lu(Db18c6)(H2O)3(thf)6]4(I3)2(I5)6(I8)(I1
Publisher: Wiley
Date: 30-07-2010
Electron Delocalization in Spectroelectrochemically and Computationally Characterized [Pt{(p-BrC6F4)NCH═C(Cl)NEt2}Cl(py)]+ Formed by Electrochemical
Publisher: American Chemical Society (ACS)
Date: 12-2021
3d–4f heterometallic complexes by the reduction of transition metal carbonyls with bulky LnII amidinates
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0DT01271H
Abstract: Heterometallic lanthanide-transition metal carbonyl complexes [Sm 2 –Co 2 ], [Yb–Co], and [Sm 2 –Fe 3 ] have been synthesized by redox reactions between bulky amidinate stabilized alent Ln and TM carbonyl complexes.
Dinitrogen Reduction and CH Activation by the Divalent Organoneodymium Complex [(C5H2tBu3)2Nd(μ‐I)K([18]crown‐6)]
Publisher: Wiley
Date: 26-01-2009
Corrosion Mitigation of Mild Steel by New Rare Earth Cinnamate Compounds
Publisher: Springer Science and Business Media LLC
Date: 06-2004
Conductances of Some Group V Quaternary 'onium Iodomercurate(II) Complexes
Publisher: CSIRO Publishing
Date: 1963
DOI: 10.1071/CH9630579
Abstract: Conductances of dilute solutions of iodomercurate(II) complexes of the stoicheiometries, M2HgI4, MHgI3, and MHg2I5 (where M is a Group V quaternary 'onium cation), in acetone have been measured. The effect of dissociation of the complexes on the conductance is discussed.
Solvent-Free Lanthanoid Complexes Derived From Chelation-Supported Organoamide Ligands
Publisher: Wiley
Date: 06-2002
DOI: 10.1002/1099-0682(200206)2002:6<1425::AID-EJIC1425>3.0.CO;2-T
Facile cleavage of pentafluorophenylmercury compounds
Publisher: Elsevier BV
Date: 07-1967
The formation of organometallic compounds by sulphur dioxide elimination reactions of the pentafluorobenzenesulphinate ion
Publisher: Elsevier BV
Date: 07-1973
Diagnosis of the nature of carboxylate coordination from the direction of shifts of carbonoxygen stretching frequencies
Publisher: Elsevier BV
Date: 10-1985
Lanthanoid Induced C–F Activation of All Fluorine Atoms of One CF3 Group
Publisher: Wiley
Date: 25-02-2015
Use of MeMn(CO)5 in the low temperature MOCVD growth of Mn containing alloys
Publisher: Elsevier BV
Date: 04-1990
Novel in situ methodology to observe the interactions of chemotherapeutical Pt drugs with DNA under physiological conditions
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4DT00861H
Abstract: The binding of the antitumor drug cisplatin with DNA was determined by means of in situ resonant inelastic X-ray scattering (RIXS) spectroscopy.
The Synthesis of a Homoleptic Lanthanoid Complex of the 8‐Quinolinolate Ion Directly from the Metal
Publisher: Wiley
Date: 10-2005
Abstract: Reaction of 8‐hydroxyquinoline (HOQ) with holmium metal in the presence strontium metal and metallic mercury at 190 °C under vacuum in a 1,3,5‐tri‐ tert ‐butylbenzene flux yielded (η 2 ‐8‐quinolinolato‐ κ : N,O (Ho(2))bis(η 2 ‐8‐quinolinolato‐ κ : N,O (Ho(1)))hexakis(μ‐( O )‐8‐quinolinolato‐ κ : N,O (Ho(1))trisholmium(III) as an 8‐hydroxyquinoline solvate ( 1 ) ( C2/c , a = 17.336(4) Å, b = 23.464(5), c = 18.038(4) Å, β = 92.92(3)°, V = 7328(3) Å 3 , R1 = 0.0622). The complex was resynthesised after preactivation of the metals by mercury and then heating them with HOQ at 190 °C.
Reductive Trapping of [(OC)5W–W(CO)5]2− in a Mixed‐Valent SmII/III Calix[4]pyrrolide Sandwich
Publisher: Wiley
Date: 14-06-2017
Abstract: Reduction of tungsten hexacarbonyl by the alent samarium(II) complex [Sm
Organothallium Compounds. XV. Thallation of Polyfluoroaromatic Compounds
Publisher: CSIRO Publishing
Date: 1979
DOI: 10.1071/CH9790737
Abstract: Thallic trifluoromethanesulfonate has been prepared by reaction of trifluoromethanesulfonic acid with either thallic oxide or solutions of thallic trifluoroacetate in trifluoroacetic acid, and has been isolated as the trihydrate on crystallization fromnitromethane. The polyfluoroarenes,p-CH3OC6F4H, p-CH3C6F4H, m-H2C6F4, o-H2C6F4, p-H2C6F4, C6F5H, 1,3,5-F3C6H3 or 1,2,4-F3C6H3, have been thallated by thallic trifluoromethanesulfonate in trifluoroacetic acid, giving the corresponding poly- fluorophenylthallium(III) bis(trifluoromethanesulfonates), which have been characterized spectroscopically and by conversion into the corresponding (polyfluoro)iodobenzenes on treatment with sodium iodide. Only slight thallation of m-BrC6F4H and m-O2NC6F4H was observed. By contrast with thallic trifluoromethanesulfonate, thallic trifluoroacetate in trifluoroacetic acid induced little thallation of the most reactive polyfluorobenzene, p-CH3OC6F4H. Thallic trifluoromethanesulfonate also thallated p-CH3OC6F4H in nitromethane, sulfolane, and with the substrate as solvent, but p-CH3C6F4H failed to react. Treatment of the polyfluorophenylthallium(III) bis(trifluoromethane- sulfonates) with boiling aqueous sodium acetate caused symmetrization into the corresponding acetatobis(polyfluorophenyl)thallium(III) compounds. A similar reaction between 2,4,6-trifluoro- phenylthallium(III) bis(trifluoromethanesulfonate) and sodium acetate at room temperature yielded 2,4,6-trifluorophenylthallium(III) diacetate. 2,3,4,6-Tetrafluorophenylthallium(III) bis(trifluor0- methanesulfonate) was converted by boiling water into bis(2,3,4,6-tetrafluorophenyl)thallium(III) trifluoromethanesulfonate.
Organolanthanoids. VI. Syntheses of cyclopentadienyllanthanoids by transmetallation reactions between thallous cyclopentadienides and lanthanoid elements
Publisher: CSIRO Publishing
Date: 1984
DOI: 10.1071/CH9840517
Abstract: Cyclopentadienyllanthanoids (C5H5)3M(thf) (M = Ce, Nd, Sm, Gd or Er thf = tetrahydrofuran), (C5H5)3M (M = Er or Yb), (MeC5H4),M (M = Nd, Sm or Gd), (C5H5)2Yb, (C5H5)2Yb(dme) (dme = 1,2-dimethoxyethane), and (MeC5H4)2Yb(thf), have been synthesized in satisfactory-to-good yield by reaction of the lanthanoid elements with the thallous cyclopentadienides (RC5H4)TI (R = H or Me) in tetrahydrofuran or 1,2-dimethoxyethane. The outcome of the reaction of ytterbium with thallous cyclopentadienide [(C5H5),Yb n = 2 or 3] depends on the stoichiometry it has been shown that (C5H5),Yb is reduced by ytterbium metal to (C5H5),Yb and that the alent compound is oxidized to (C5H5),Yb by thallous cyclopentadienide. Addition of mercury metal aids initiation of transmetallation, but it is not essential for reaction to occur.
Organomercury compounds. XII. The synthesis of diarylmercurials and arylmercuric arenesulphinates by sulphur dioxide elimination reactions
Publisher: CSIRO Publishing
Date: 1971
DOI: 10.1071/CH9711599
Abstract: The diarylmercurials, R2Hg [R = Ph, p-XC6H4 (X = Me, Br, Cl, or F), 2,3,4-Cl3C6H2, 2,4,5-Cl3C6H2, 2-naphthyl, or 8-quinolyl], have been prepared in satisfactory yield by sulphur dioxide elimination reactions on heating the corresponding mercuric arenesulphinates under vacuum, but decomposition of mercuric p-acetamidobenzenesulphinate gave acetanilide. The mercuric arenesulphinates were obtained by reaction of mercuric acetate with the appropriate sodium arenesulphinates in aqueous solution at room temperature. Similar reactions in boiling aqueous solution gave either diarylmercurials, R2Hg [R = Ph, p-XC6H4 (X = Me, F, or MeCONH), 2,4,6-Me3C6H2, 2,4,6-(Me2CH)3C6H2, or 8-quinolyl], or arylmercuric arenesulphinates, RHg(02SR) [R = p-XC6H4 (X = Br or Cl), 2,3,4-Cl3C6H2, 2,4,5-Cl3C6H2, or 2-naphthyl], usually in low yield, and sulphur dioxide. Mercury-carbon bond formation also occurred in reactions of mercuric acetate with sodium mesitylenesulphinate and 2,4,6-triisopropylbenzenesulphinate at room temperature, mesitylmercuric mesitylenesulphinate and bis(2,4,6- triisopropylphenyl)mercury, respectively, being obtained. The sulphur- oxygen stretching frequencies of the mercuric arenesulphinates are indicative of S-sulphinate coordination, whilst those of the arylmercuric arenesulphinates are consistent with unidentate O- sulphinate groups.
Nitrile Functionalized Methimazole-Based Ionic Liquids
Publisher: American Chemical Society (ACS)
Date: 16-11-2010
DOI: 10.1021/JO101449Q
Abstract: The alkylation reaction of 2-mercapto-1-methylimidazole 1b with 2-chloroacetonitrile and 2-chloropropionitrile produced S-alkyl methimazole chlorides 2a and 2b which were subjected to anion metathesis with lithium bis(trifluoromethanesulfonyl)amide, LiNTf(2), to afford nitrile functionalized methimazole-based room temperature ionic liquids 3a and 3b in 94% and 89% yields, respectively. Ionic liquids 3a and 3b have reasonably wide electrochemical windows. The efficient extraction of Ag(+) from aqueous media into 3a and 3b is also reported.
Structure and magnetism of a mixed-valence octanuclear manganese(ii /iii ) cluster derived from carbamoylcyanonitrosomethanide (ccnm)
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2DT32303F
Abstract: A mixed-valence octanuclear manganese complex of formula [Mn(II)(4)Mn(III)(4)O(4)(ccnm)(12)]·4MeCN·7H(2)O (1·4MeCN·7H(2)O) (ccnm = carbamoylcyanonitrosomethanide) has been synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and magnetic measurements. The metal core of 1 adopts a tetra-capped (with Mn(II) ions) distorted [Mn(III)(4)O(4)](4+) cubane topology, with a three-J magnetic analysis indicating that the cluster displays dominant antiferromagnetic interactions. Three equally possible fits were obtained, all leading to a spin ground state of S = 0 with S = 1, 2 and 3 close in energy. Comparisons of the magnetic analysis are made with that published for a related Mn(8) cluster and, more generally, with other Mn(III)Mn(III) and Mn(III)Mn(II) fragments in clusters of various types.
Crystal structure of chloro(1,2,5,6-η-cycloocta-1,5-diene)phenylplatinum(II), (C6H5)(C8H12)PtCl
Publisher: Walter de Gruyter GmbH
Date: 02-1993
Exploring the reactivity of L-tellurocystine, Te-protected tellurocysteine conjugates and diorganodiselenides towards hydrogen peroxide: synthesis and molecular structure analysis
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2NJ00997H
Abstract: The synthesis of a series of novel organotellurium species and diorganoselenones is reported.
Manipulation of reaction pathways in redox transmetallation–ligand exchange syntheses of lanthanoid(ii )/(iii ) aryloxide complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B511609K
Abstract: Redox transmetallation/ligand exchange reactions of lanthanoid metals (Ln), Hg(C6F5)2 and HOAr(OMe) (Ar(OMe) = C6H2-2,6-Bu(t)-4-OMe), in thf (tetrahydrofuran) gave, for Ln = Yb, [Yb(OAr(OMe))2(thf)3], and for Ln = Sm, a mixture of [Sm(II)(OAr(OMe))2(thf)3] and mainly [Sm(III)(Ar(OMe))3(thf)] x thf. X-Ray structure determinations show the alent complexes to have distorted square-pyramidal stereochemistry with transoid thf and OAr(OMe) ligands in the basal plane. Treatment of [Yb(OAr(OMe))2(thf)3] with diethyl ether or PhMe at room temperature gave [Yb(OAr(OMe))2] or [Yb(OAr(OMe))2] x 0.5 PhMe. For lanthanoids Ln = Nd, Er or Y, the reactions with Hg(C6F5)2 and HOAr(OMe) yielded complex product mixtures, from one of which the novel erbium aryloxide fluoride cage [Er3(OAr(OMe))4(mu2-F)3(mu3-F)2(thf)4] x thf x 0.5 C6H14 was isolated. The cage core consists of a triangle of Er atoms joined to two mu3-fluoride ligands and three further mu2-fluorides bridge adjacent Er atoms. One of the Er atoms is six-coordinate with additionally two OAr(OMe) ligands whilst the other two have one OAr(OMe) and two thf ligands and are seven coordinate. Substitution of Hg(C6F5)2 by Hg(CCPh)2 in the redox transmetallation/ligand exchange reactions gave the new derivatives [Ln(OAr(OMe))3(thf)] x thf (Ln = La, Pr, Nd, Sm, Gd, Ho) in good yields whilst Ln = Yb gave [Yb(OAr(OMe))2(thf)3]. Recrystallisation of [Sm(OAr(OMe))3(thf)] x thf from dme (1,2-dimethoxyethane) yielded [Sm(OAr(OMe))3(dme)]. Structural characterisation of [Ln(OAr(OMe))3(thf)] x thf (Ln = Nd, Ho) and [Sm(OAr(OMe))3(dme)] showed monomeric four-coordinate distorted tetrahedral and five-coordinate distorted square-pyramidal complexes respectively. For the smaller lanthanoids Ln = Y, Er or Lu, reactions with Hg(CCPh)2 and HOAr(OMe) gave the mixed aryloxide/alkynide complexes [Ln(OAr(OMe))2(CCPh)(thf)2]. Oxidation of the alent ytterbium aryloxide [Yb(OAr(OMe))2(thf)3] by Hg(CCPh)2 in thf gave the analogous [Yb(OAr(OMe))2(CCPh)(thf)2]. The erbium alkynide [Er(OAr(OMe))2(CCPh)(thf)2] x 0.25 C6H14 has distorted square-pyramidal stereochemistry with transoid OAr(OMe) and thf ligands in the basal plane and a rare (for Ln) terminal alkynide ligand in the apical position. The reactive Lu-C bond in the [Lu(OAr(OMe))2(CCPh)(thf)2] complexes could be slowly cleaved by free HOAr(OMe) in hydrocarbon solvents, yielding Lu(OAr(OMe))3 species and fortuitous partial hydrolysis of [Er(Ar(OMe))2(CCPh)(thf)2] gave the dimeric [Er(OAr(OMe))2(mu-OH)2]2.
Syntheses of organonickel compounds by decarboxylation reactions
Publisher: Elsevier BV
Date: 12-1971
Symmetrization of bispolyfluorophenylthallium(III) compounds
Publisher: Elsevier BV
Date: 1975
Synthesis of Ruthenium(II) Carbonyl Chloride Complexes Containing N-Donor Bidentate Ligands
Publisher: Informa UK Limited
Date: 1986
Exploring the effect of the LnIII/LnIIredox potential on C–F activation and on oxidation of some lanthanoid organoamides
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5DT04239A
Abstract: The role of the Ln II oxidation state (Ln = Eu, Yb, Sm) in C–F activation reactions has been explored.
The effect of anion fluorination in ionic liquids—physical properties of a range of bis(methanesulfonyl)amide salts
Publisher: Royal Society of Chemistry (RSC)
Date: 2003
DOI: 10.1039/B304072K
Organomercury Compounds
Publisher: Elsevier BV
Date: 02-1973
Hydrated Rare Earth Structural Networks containing the Phenylene‐1, 2‐dioxydiacetate (PDDA) Ligand
Publisher: Wiley
Date: 12-12-2012
Organoamido- and Aryloxo-lanthanoids. IX. Preparations and Structures of Tris(η2-3,5-diphenyl-pyrazolato)lanthanoid(III) Complexes With Triphenylphosphine Oxide and Tetrahydrofuran
Publisher: CSIRO Publishing
Date: 1993
DOI: 10.1071/CH9931881
Abstract: From reaction of lanthanoid metals with bis ( pentafluorophenyl )mercury and 3,5-diphenylpyrazole (HPh2pz) in 1,2-dimethoxyethane ( dme ) and treatment of the products with triphenylphosphine oxide, the complexes [ Ln (η2-Ph2pz)3(OPPh3)2].( dme )n ( Ln = Er or Nd , n = 1 Ln = La, n = 0.6) have been isolated. An X-ray crystal structure shows that the erbium complex [monoclinic, space group C2, a 22.08(3), b 14.30(1), c 13.37(1) Ǻ, β 124.09(7)°, Z 2 2730 'observed' data refined to R 0.046] is monomeric , with eight coordination of the metal. There is a trigonal bipyramidal arrangement of the centre ( Cen ) of the N-N bonds of three η2-3,5-diphenylpyrazolate groups ( ΣCen-Er-Cen 360° ( Er -N) 2.344 Ǻ) and the oxygens of two equivalent trans triphenylphosphine oxide ligands [O- Er -O 176(1)° Er -O 2.207(9)Ǻ]. Unit cell data indicate that the neodymium analogue [monoclinic, space group C2, a 23.01(3), b 14.94(2), c 13.82(2) Ǻ, β 123.65(8)°] is isostructural with the erbium complex. An analogous reaction of lanthanum or neodymium metal, Hg(C6F5)2, and HPh2pz in tetrahydrofuran ( thf ) gives [ Ln (η2-Ph2pz)3( thf )3]. thf ( Ln = La or Nd ). The X-ray crystal structure of the neodymium complex [orthorhombic, space group P212121, a 14.009(9), b 16.280(8), c 22.640(16)Ǻ, Z 4, 2967 'observed' data refined to R 0.046 reveals a nine-coordinate monomer with three η2-Ph2pz ligands [ Nd -N 2.420(10)-2.524(8)Ǻ] and three thf ligands [ Nd -O 2.497(8)-2.587(8)Ǻ]. There is a trigonal prismatic arrangement of the centres of the N-N bonds and the oxygen donor atoms.
Organomercury compounds. XIII. The mercuration of 1,2,4,5-tetrafluorobenzene
Publisher: CSIRO Publishing
Date: 1972
DOI: 10.1071/CH9720057
Abstract: 2,3,5,6.Tetrafluorophenylmercuric trifluoroacetate and acetate, 1,4-bis(tri-fluoroacetatomercuri)tetrafluorobenzene, and 1,4-di(acetatomercuri)tetraffuorobenzene have been prepared by mercuration of 1,2,4,5-tetrafluorobenzene with mercuric trifluoroacetate or acetate while 2,3,5,6-tetrafluorophenglmercuric chloride and acetate, 1,4-di(chloromercuri)tetrafluorobenzene, and 1,4-di(acetatomercuri)tetrafluorobenzene have been obtained from the corresponding trifluoroacetates by metathesis reactions. The di(chloromercuri) derivative has also been isolated from reaction of thallous tetrafluoroterephthalate with mercuric chloride. Bis(2,3,5,6-tetrafluorophenyl)mercury has been prepared by rearrangement of 2,3,5,6-tetrafluorophenglmercuric trifluoroacetate with iodide ions, and by mercuration of 1,2,4,5-tetrafluorobenzene with tetrabromomercurate(11) ions under alkaline conditions. The latter reaction also gave a low yield of 1,4-bis(2,3,5,6-tetrafluorophenylmercuri)tetrafluorobenzene, which was identified by N.M.R. spectroscopy, and by degradation with mercuric chloride. The carbon-oxygen stretching frequencies of the new organomercuric carboxylates are indicative of unidentate carboxylate coordination.
Heavy Alkaline Earth Metal Pyrazolates: Synthetic Pathways, Structural Trends, and Comparison with Divalent Lanthanoids
Publisher: Wiley
Date: 24-06-2004
Abstract: Two series of heavy alkaline earth metal pyrazolates, [M(Ph(2)pz)(2)(thf)(4)] 1 a-c (Ph(2)pz=3,5-diphenylpyrazolate, M=Ca, Sr, Ba THF=tetrahydrofuran) and [M(Ph(2)pz)(2)(dme)(n)] (M=Ca, 2 a, Sr, 2 b, n=2 M=Ba, 2 c, n=3 DME=1,2-dimethoxyethane) have been prepared by redox transmetallation/ligand exchange utilizing Hg(C(6)F(5))(2). Compounds 1 a and 2 b were also obtained by redox transmetallation with Tl(Ph(2)pz). Alternatively, direct reaction of the alkaline earth metals with 3,5-diphenylpyrazole at elevated temperatures under solventless conditions yielded compounds 1 a-c and 2 a-c upon extraction with THF or DME. By contrast, [M(Me(2)pz)(2)(Me(2)pzH)(4)] 3 a-c (M=Ca, Sr, Ba Me(2)pzH=3,5-dimethylpyrazole) were prepared by protolysis of [M[N(SiMe(3))(2)](2)(thf)(2)] (M=Ca, Sr, Ba) with Me(2)pzH in THF and by direct metallation with Me(2)pzH in liquid NH(3)/THF. Compounds 1 a-c and 2 a-c display eta(2)-bonded pyrazolate ligands, while 3 a,b exhibit eta(1)-coordination. Complexes 1 a-c have transoid Ph(2)pz ligands and an overall coordination number of eight with a switch from mutually coplanar Ph(2)pz ligands in 1 a,b to perpendicular in 1 c. In eight coordinate 2 a,b the pyrazolate ligands are cisoid, whilst 2 c has an additional DME ligand and a metal coordination number of ten. By contrast, 3 a,b have octahedral geometry with four eta(1)-Me(2)pzH donors, which are hydrogen-bonded to the uncoordinated nitrogen atoms of the two trans Me(2)pz ligands. The application of synthetic routes initially developed for the preparation of lanthanoid pyrazolates provides detailed insight into the similarities and differences between the two groups of metals and structures of their complexes.
New Structural Features in Heavy Alkaline Earth‐Metal Chemistry — Molecular Heterobimetallic Group 1, Ba Complexes
Publisher: Wiley
Date: 08-02-2007
Abstract: The preparation of heterobimetallic complexes consisting of alkali and heavy alkaline earth metals remains a challenge due to limited available synthetic strategies. Here we present a new class of group 1, Ba compounds of the type [M(n){Ba(Odpp)(2+n)}] (M=Na(n=1) (1), K(n=1) (2), Cs(n=1) (3), Li(n=2) (4) HOdpp=2,6-diphenylphenol) and the Lewis base adducts [Li(2)(thf)(2){Ba(Odpp)(4)}]PhMe (5) and [K{Ba(Odpp)(3)(diglyme)}] (6) (diglyme=[bis(2-methoxy)ethyl ether]) as the first representatives of heterobimetallic group 1, Ba species of low nuclearity. The compounds display a significant degree of metal-arene interaction, believed to be a key factor in stabilizing these highly reactive species. Obtained by solid-state direct metalation, the target compounds are available without further work-up.
Homoleptic 12-coordinate lanthanoids with η2-nitroso ligands
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B702473H
Abstract: The complexes [Et(4)N](3)[Ln(eta(2)-dcnm)(6)] (Ln = La, Ce, Nd, Gd, dcnm = dicyanonitrosomethanide) have discrete N, O 12-coordination owing to symmetrical chelation of the nitroso donor groups.
Systematic differences in electrochemical reduction of the structurally characterized anti-cancer platinum(IV) complexes [Pt{((p-HC6F4)NCH2)2}-(pyridine)2Cl2], [Pt{((p-HC6F4)NCH2)2}(pyridine)2(OH)2],
Publisher: Elsevier BV
Date: 10-2012
DOI: 10.1016/J.JINORGBIO.2012.07.016
Abstract: The putative platinum(IV) anticancer drugs, [Pt{((R)NCH(2))(2)}(py)(2)XY] (X,Y=Cl, R=p-HC(6)F(4) (1a), C(6)F(5) (1b) X,Y=OH, R=p-HC(6)F(4) (2) X=Cl, Y=OH, R=p-HC(6)F(4) (3), py = pyridine) have been prepared by oxidation of the Pt(II) anticancer drugs [Pt{((R)NCH(2))(2)}(py)(2)] (R=p-HC(6)F(4) (4a) or C(6)F(5) (4b)) with PhICl(2) (1a,b), H(2)O(2) (2) and PhICl(2)/Bu(4)NOH (3). NMR spectroscopy and the X-ray crystal structures of 1b, 2 and 3 show that they have octahedral stereochemistry with the X,Y ligands in the trans-position. The net two electron electrochemical reduction of 1a, 2 and 3 has been studied by voltammetric, spectroelectrochemical and bulk electrolysis techniques in acetonitrile. NMR and other data reveal that reduction of 1a gives pure 4a via the elimination of both axial chloride ligands. In the case of 2, one end of the diamide ligand is protonated and the resulting -NH(p-HC(6)F(4)) group dissociated giving a [Pt{N(p-HC(6)F(4))CH(2)CH(2)NH(p-HC(6)F(4))}] arrangement, one pyridine ligand is lost and a hydroxide ion retained in the coordination sphere. Intriguingly, in the case of reduction of 3, a 50% mixture of the reduction products of pure 1a and 2 is formed. The relative ease of reduction is 1>3>2. Testing of 1a, 2 and 3 against L1210 and L1210(DDP) (DDP = cis-diamine-dichloroplatinum(II)) mouse leukaemia cells shows all to be cytotoxic with IC(50) values of 1.0-3.5 μM. 2 and 3 are active in vivo against AHDJ/PC6 tumor line when delivered in peanut oil despite being hard to reduce electrochemically, and notably are more active than 4a delivered in this medium whilst comparable with 4a delivered in saline/Tween.
Synthesis and Structures of Homoleptic Monomeric Potassium Aryloxolanthanoidate(III) Complexes
Publisher: Wiley
Date: 23-03-2005
Theoretical and Experimental Insights into the Mechanism of the Nucleophilic Addition of Water and Methanol to Dicyanonitrosomethanide
Publisher: American Chemical Society (ACS)
Date: 18-11-2010
DOI: 10.1021/JP108550Z
Abstract: In this work the nucleophilic addition of water and methanol to the dicyanonitrosomethanide anion (dcnm, [C(CN)(2)(NO)](-)) in the absence of the usual transition metal promoters was investigated. Experimentally it was shown that a quantitative conversion of the dcnm anion to carbamoylcyanonitrosomethanide (ccnm, [C(CN)(CONH(2))(NO)](-)) by the addition of 1 equiv of water to a nitrile group is complete in 48 h at 100 °C, or in 1.5 h at 150 °C when the reaction is conducted in a microwave reactor. Attempts to add a second equivalent of water to the anion failed with thermal degradation of the anion occurring at 200 °C. Ab initio calculations show that the reaction proceeds via three distinct transition states: (1) the transfer of a proton from a water molecule to the nitrile group, (2) the subsequent attack of the generated hydroxide anion on the carbon atom of the nitrile group, and (3) a rapid proton transfer to form a carbamoyl group. The attacking water molecule is shown to be a stronger proton donor when modeled as part of a hydrogen-bonded three water molecule chain, leading to a significant reduction in the reaction barrier. Only the anti-ccnm anion is formed in the reaction. There is a high-energy barrier to the formation of the syn isomer by the rotation of the nitroso group. While the syn isomer of ccnm is shown to be the more thermodynamically stable conformation, examination of the HOMO-1 molecular orbital that arises during the second transition state of the reaction indicates the addition of the hydroxide anion to the carbon atom is forbidden due to orbital symmetry, with a similar effect responsible for the failure of a second equivalent of water to add to the ccnm anion. Under analogous reaction conditions the addition of 1 equiv of methanol to dcnm to form cyano(imino(methoxy)methyl)nitrosomethanide (cmnm, [C(CN)(C(OMe)NH)(NO)](-)) failed, although ab initio calculations initially indicated the reaction should proceed more readily than the addition of water. When the energy required to break the hydrogen-bonded cyclic hexamers in methanol is taken into consideration, the energy barrier to the first transition step is greatly increased. The addition of a second equivalent of methanol to cmnm is unlikely to occur even in the presence of a transition metal as the resultant anion would be marginally thermodynamically unstable.
Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination
Publisher: Elsevier BV
Date: 10-1980
The chemistry and complexes of small cyano anions
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1CC11909E
Abstract: The chemistry of the anions dicyanamide and tricyanomethanide (dca and tcm, respectively) has produced a plethora of discoveries over the past few decades, particularly in relation to transition-metal coordination polymers with magnetic coupling. Over recent years there have been an increasing number of reports of heterofunctionalised cyano-containing anions, typically derivatives of dicyanomethanide. Our own group has been particularly concerned with the amide- and nitroso-functionalised anions carbamoyldicyanomethanide (cdm) and dicyanonitrosomethanide (dcnm), respectively. This feature article examines the fascinating ersity of materials and complexes that can be obtained using small cyano anions, ranging from coordination polymers to heterometallic clusters and hydrogen bonding networks. In particular, we focus on results from our own laboratories in the past few years. The magnetic properties of these materials are briefly discussed.
Organomercury compounds
Publisher: Elsevier BV
Date: 05-1968
[Yb(THF)3(C5H4PPh2)2W(CO)4]·0.5THF and 1[Yb(THF)(C5H4PPh2)2(μ-OC)W(CO)3]: Two New Heterobimetallic Complexes Containing YbII and W0
Publisher: Wiley
Date: 12-2002
DOI: 10.1002/1099-0682(200212)2002:12<3172::AID-EJIC3172>3.0.CO;2-Q
Preparation and structure of μ-(2,2′-dipyridylamido-Nα,N:N′)-μ-(2″,2‴-dipyridylamido-Nα′,N″:N‴)bis {bis(pentafluorophenyl)thallium(III)} unexpected formation of a four membered chelate ring
Publisher: Elsevier BV
Date: 1977
Organomercury compounds. Part V. Preparations of pentachlorophenylmercury compounds by decarboxylation reactions
Publisher: Royal Society of Chemistry (RSC)
Date: 1967
DOI: 10.1039/J39670002313
Frontispiece: Can Bismuth Replace Mercury in Redox Transmetallation/Protolysis Syntheses from Free Lanthanoid Metals?
Publisher: Wiley
Date: 27-11-2018
Bistetrachloronitrophenylmercury compounds
Publisher: CSIRO Publishing
Date: 1975
DOI: 10.1071/CH9751499
Abstract: The bistetrachloronitrophenylmercurials R2Hg (R = o-, m- or p-O2NC6Cl4) have been prepared by mercuration of the appropriate tetrachloronitrobenzenes with mercuric trifluoroacetate under forcing conditions. Bis(2,3,5,6-tetrachloro-4-nitrophenyl)mercury could not be obtained analytically pure by this method, but pyrolysis of mercuric 2,3,5,6-tetrachloro-4-nitrobenzenesulphonate gave the pure mercurial. Sodium 2,3,5,6-tetrachloro-4-nitrobenzenesulphonate was prepared by reaction of 2,3,5,6- tetrachloro-1,4-dinitrobenzene with sodium sulphite, and was converted into the mercuric salt via the barium salt and free sulphonic acid. Cleavage of the bistetrachloronitrophenylmer- curials with iodine in N,N-dimethylformamide gave the corresponding tetrachloroiodonitrobenzenes. When the mercurials were cleaved with triiodide ions, the resulting tetrachloroiodonitrobenzenes contained impurities, e.g. tetrachloronitrobenzenes or tetrachlorodiiodobenzenes, which were formed by reaction of iodide ions (derived from I3-) either with the mercurials or with their cleavage products.
Lanthanoid Pseudo‐Grignard Reagents: A Major Untapped Resource
Publisher: Wiley
Date: 05-12-2017
Abstract: Pseudo-Grignard reagents PhLnI (Ln=Yb, Eu), readily prepared by the oxidative addition of iodobenzene to ytterbium or europium metal at -78 °C in tetrahydrofuran (THF) or 1,2-dimethoxyethane (DME), react with a range of bulky N,N'-bis(aryl)formamidines to generate an extensive series of Ln
Isolation of the novel example of a monomeric organotellurinic acid
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9DT04013G
Abstract: The synthesis of the first ex le of a monomeric, stable organotellurinic acid is reported by utilizing the σ-hole participation of the Te atom with the N atom of the 2-(2′-pyridyl)phenyl moiety.
Coordination derivatives and reactions of dichloropentafluorophenylindium
Publisher: CSIRO Publishing
Date: 1974
DOI: 10.1071/CH9742547
Abstract: The complexes C6F5InCl2,L [L = N,N,N?,N?-tetramethylethylenediamine (tmed), 2,2?-bipyridyl (bpy), 1,10-phenanthroline (phen), 2,2?:6?,2?- terpyridyl (tpy) or (Ph2PCH2)2] have been prepared by reaction of C6F5InCl2,diox (diox = 1,4-dioxan) with the appropriate ligands, and are considered to contain five-coordinate indium on the basis of indium- chlorine stretching frequencies. Monomeric structures are likely for all complexes except C6F5InCl2,tmed, which is dimeric with bridging tmed. Atmospheric moisture converts C6F5InCl2,L (L = phen or tpy) into monohydrates, in which water is not coordinated. Reaction of C6F5InCl2,diox with pyridine, triphenylphosphine and dimethyl sulphoxide causes quantitative rearrangement into the corresponding indium trichloride and tris-pentafluorophenylindium complexes. The derivatives (C6F5)nIn(ox)3-n(n = 1 or 2 ox = quinolin-8-olate) have been prepared by cleavage of (C6F5)3In,diox with quinolin-8-ol, and C6F5In(ox)2 has also been obtained from C6F5InCl2,diox and thallous quinolin-8-olate.
4-Hydroxybenzoato-rare earth(iii) complexes – syntheses, a structural goldmine from coordination diversity and improved corrosion inhibition behaviour
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3NJ02735J
Abstract: A range of rare earth( iii ) 4-hydroxybenzoato (4hob) complexes has been prepared and structurally characterized. The La, Ce and Y complexes are good corrosion inhibitors for mild steel.
More than Steric Effects: Unlocking the Coordination Chemistry of Barium Pyrazolates
Publisher: Wiley
Date: 19-12-2007
Abstract: To further our understanding of the coordination chemistry of the heavy alkaline earth metals, we here report on a family of barium pyrazolates bearing various substitution patterns that illustrate the delicate balance between ligand bulk, donor size, stoichiometry, and hapticity, while emphasizing the importance of secondary interactions including π‐bonding, agostic interactions, and hydrogen bonding to stabilize these heavy‐metal complexes. The dimeric compounds [{Ba(Me 2 pz) 2 (pmdta)} 2 ] ( 1 ), [{Ba(Phpz) 2 (pmdta)} 2 ] ( 2 ), [{Ba( t Bupz) 2 (pmdta)} 2 ] ( 3 ), [{Ba(MePhpz) 2 (tmeda)} 2 ] ( 5 ), [{Ba(Ph 2 pz) 2 (tmeda)} 2 ] · TMEDA ( 6 ), the polymer [{Ba( t Bupz) 2 (NH 3 ) 2 } n ] ( 4 ), and the monomer [Ba(Ph 2 pz) 2 (tmeda) 2 ] · TMEDA ( 7 ), were prepared using a variety of synthetic methods and were characterized spectroscopically and structurally. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Structural versatility in hydrated rare earth(iii) 1,2-benzenedisulfonates
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B614681C
Actions and discourses for transformative understanding in a middle school science class
Publisher: Informa UK Limited
Date: 03-2001
Bis(pentafluorophenyl)(N,N,N',N'-tetramethylethylenediamine)platinum(II)
Publisher: International Union of Crystallography (IUCr)
Date: 15-09-1991
Preparations, sulphinate coordination, and thermal decomposition of some bismuth triarenesulphinates
Publisher: CSIRO Publishing
Date: 1972
DOI: 10.1071/CH9722107
Abstract: Bismuth triarenesulphinates, Bi(02SR)3 [R = Ph, p-MeC6H4, p-ClC6H4, 2,4,6-(Me2CH)3C6H2, and p-MeCONHC6H4], have been prepared by reaction of bismuth triacetate with the appropriate arenesulphinio acids in glacial acetic acid, and the first two compounds have also been obtained by reaction of triphenyl-bismuth with the appropriate mercuric arenesulphinates. The sulphur-oxygen stretching frequencies of the bismuth sulphinates are indicative of O-sulphinate coordination, and the compounds are considered to be polymeric with bridging O-sulphinate groups and six-coordinate bismuth. Thermal decomposition of Bi(O2SR)3 (R = Ph, p-MeC6H4, or p-CIC6H4) under vacuum gave the corresponding triarylbismuth compounds and sulphur dioxide, the preparation of tri-p-chlorophenylbismuth being accompanied by formation of di-p-chlorophenyl sulphone and S-p-chlorophenyl p-chlorobenzenethiosulphonate. Pyrolysis of the other triarenesulphinates did not yield organobismuth compounds.
1139. The chemistry of organothallium compounds. Part II. The complexes of bis(pentafluorophenyl)thallium(III) compounds with some neutral unidentate ligands
Publisher: Royal Society of Chemistry (RSC)
Date: 1965
DOI: 10.1039/JR9650006107
Volatilisation of methyl-mercuric chloride by hydrogen sulphide
Publisher: Springer Science and Business Media LLC
Date: 09-1978
DOI: 10.1038/275344A0
Mechanism of hydrolysis of a platinum(IV) complex discovered by atomic telemetry
Publisher: Elsevier BV
Date: 10-2018
DOI: 10.1016/J.JINORGBIO.2018.07.012
Abstract: Herein we report on the hydrolysis mechanism of [Pt{N(p-HC
Complexes of Four‐Membered Group 13 Metal(I) N‐Heterocyclic Carbene Analogues with Metal Carbonyl Fragments
Publisher: Wiley
Date: 08-2009
A supramolecular approach to the examination of the structures of some anticancer organoamidoplatinum(II) complexes
Publisher: Informa UK Limited
Date: 06-12-2017
Synthesis and metal complexes of symmetrically N-substituted bispidinones
Publisher: Elsevier BV
Date: 02-1995
Organomercury compounds. XI. Some coordination derivatives of bispentafluorophenylmercury
Publisher: CSIRO Publishing
Date: 1971
DOI: 10.1071/CH9710489
Abstract: The complexes (C6F5)2HgL (L = 4,4?-dimethyl-2,2?-bipyridyl, 2,2?- biquinolyl, 2,2?:6?,2?-terpyridyl, 2,4,7,9,-tetramethyl-1,10- phenanthroline, ethylenediamine, o-phenylenediamine, diphenylamine, pyridine, 4-cyanopyridine, triphenylphosphine, triphenylphosphine oxide, or 1,2-bisdiphenylarsinoethane), (C6F5)2HgL2 (L = di-2- pyridylamine), and [(C6F5)2Hg]2L (L = bisdiphenylphosphinomethane or bisdiphenyl-arsinomethane) have been prepared, and their constitution, solution stabilities, and structures studied, together with those of the known complexes (C6F5)2HgL (L = 2,2?- bipyridyl, 1,10-phenanthroline, or 1,2-bisdiphenylphosphinoethane). Coordination of triphenylarsine oxide to bispentafluorophenylmercury in solution has also been detected, but the complex could not be isolated.
Lanthanide Formamidinates as Improved Catalysts for the Tishchenko Reaction
Publisher: Wiley
Date: 15-01-2008
The preparation of complexes of phenylmercuric chloride
Publisher: Elsevier BV
Date: 02-1968
The pathfinder image-guided surgical robot
Publisher: SAGE Publications
Date: 25-09-2010
Abstract: This paper first describes the workflow of the Pathfinder image-guided surgical robot that has been designed to replace the stereotactic frame in neurosurgery, and then details the calibration stages employed in order to achieve submillimetre positioning accuracy of a tool tip. The process uses non-linear parameter identification techniques in conjunction with some procedures for camera calibration, which exploit the fact that the camera is mounted to a calibrated robot arm that executes precise motions.
ATR characterisation of synergistic corrosion inhibition of mild steel surfaces by cerium salicylate
Publisher: Elsevier BV
Date: 11-2002
Synthesis and crystal structure of lithium alendronate
Publisher: Informa UK Limited
Date: 13-12-2010
Trispentafluorophenylindium compounds
Publisher: Elsevier BV
Date: 04-1971
Bis(pentafluorophenyl)ytterbium: A transmetallation synthesis of a σ-bonded lanthanide organometallic compound
Publisher: Elsevier BV
Date: 05-1976
Unexpected C−F activation during redox transmetallation with silver N,N′‐bis(2,6‐difluorophenyl)formamidinate
Publisher: Wiley
Date: 24-08-2022
Abstract: The trivalent lanthanoid formamidinates, [Yb 2 (DFForm) 4 F 2 (py) 2 ] ⋅ CH 3 CN ( 1 ) (DFForm= N,N ′‐bis(2,6‐difluorophenyl)formamidinate), and [La 6 (DFForm) 8 F 8 O(CH 3 CN) 2 ] ⋅ 6CH 3 CN ( 2 ) have been prepared from redox transmetallation (RT) reactions employing lanthanoid metals and silver formamidinate (AgDFForm) in CH 3 CN. C−F activation was observed in both reactions. The structure of 1 is a fluorine bridged dimer with two seven‐coordinate ytterbium metal ions. Surprisingly the lanthanum complex is a trivalent cage with an unexpected central oxygen atom. [La 6 (DFForm) 8 F 8 O(CH 3 CN) 2 ] ⋅ 6CH 3 CN ( 2 ) formed a 15 membered ring cage of six La atoms, eight F and one O at the centre. There are three different La 3+ ions in 2 with two different coordination numbers. All the La atoms are coordinated by four bridging fluorides and the central oxygen.
Organolanthanoids XXIII complexes of tris(cyclopentadienyl)lanthanoids with tertiary phosphine oxides and the X-ray crystal structures of [YbCp3(OPPh3)] and [NdCp3(OPBun3)]
Publisher: Elsevier BV
Date: 08-1998
The mercuration route to pentafluorophenylmercury compounds
Publisher: Elsevier BV
Date: 09-1967
Crystal structure of bis(2-nitrophenyl)(N,N,N′,N′-tetramethylethylenediamine)platinum(II), [(CH3)2NCH2CH2N(CH3)2](C6H4
Publisher: Walter de Gruyter GmbH
Date: 02-1993
Synthesis and structural characterisation of heavy alkaline earth N,N′-bis(aryl)formamidinate complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B602210C
Abstract: Treatment of calcium or strontium with 2.0 equivalents of N,N-bis(o-methylphenyl)formamidine (o-TolFormH), N,N-bis(2,6-dimethylphenyl)formamidine (XylFormH) or N,N-bis(o-phenylphenyl)formamidine (o-PhPhFormH) in the presence of 1.0 equivalent of Hg(C6F5)2 in tetrahydrofuran (thf) affords the bis(formamidinate) complexes [Ca(o-TolForm)2(thf)2] (1), [Ca(XylForm)2(thf)2] (2), [Ca(o-PhPhForm)2(thf)2].thf (3), [Sr(o-TolForm)2(thf)3] (4), [Sr(XylForm)2(thf)3].3thf (5) and [Sr(o-PhPhForm)2(thf)3].2thf (6). Analogous reactions with barium were generally unsatisfactory but [Ba(o-PhPhForm)2(thf)3].2thf (7) was successfully prepared. Compounds 1-7 have been characterised by various spectroscopic methods (1H, 13C{1H} NMR and IR), elemental analyses and, for 1, 2 and 4-6, X-ray crystallography. The calcium complexes are monomeric and six-coordinate with either transoid octahedral or trigonal prismatic geometry, whilst the larger radius of strontium accommodates an additional thf solvent donor to give seven-coordinate structures with two types of coordination polyhedra.
Steric control of the reduction of carbodiimides by samarium(ii) and the synthesis of very crowded samarium(iii) complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B922031C
Abstract: Reduction of N,N'-di(2,6-diisopropylphenyl)carbodiimide (DippNCNDipp) by [SmL(2)(thf)(2)] (1) (L = N,N'-bis(2,6-diisopropylphenyl)formamidinate, DippNC(H)NDipp) in PhMe gave [Sm(L)(3)] (2) in good yield. An analogous reaction of 1 with N,N'-dimesitylcarbodiimide (MesNCNMes) gave [SmL(2)(MesNC(H)NMes)] (3). In contrast, reduction of N,N'-dicyclohexylcarbodiimide (CyNCNCy) by 1 in PhMe gave mixture of products from which [SmL(2)(CyNC(CH(2)Ph)NCy)] (4) and [SmL(2)(CyNC(H)NCy)] (5) were isolated by fractional crystallisation. Using thf as the reaction solvent, solely compound 5 was crystallised. Reactions of [Sm(L)(2)(C[triple bond]CPh)(thf)] (6) with the carbodiimides RNCNR (R = Cy, Mes) gave [Sm(L)(2)(RNC(C[triple bond]CPh)NR)] (R = Cy (7) or Mes (8)) which are analogues of 4. No reaction was observed between 6 and DippNCNDipp.
Crystal structure of (1,2,5,6-η-cycloocta-1,5-diene)diphenylplatinum(II), (C6H5)2(C8H12)Pt
Publisher: Walter de Gruyter GmbH
Date: 02-1993
Organomercury compounds XX Reactions of lithium polyfluorobenzenesulphinates with mercuric salts
Publisher: Elsevier BV
Date: 04-1975
Organoaluminum and ‐gallium Formamidinate Complexes
Publisher: Wiley
Date: 08-03-2013
Synthetic routes to homoleptic and heteroleptic ruthenium(II) complexes incorporating bidentate imine ligands
Publisher: Elsevier BV
Date: 07-2004
The preparation and reactivity of arylbismuth(III) dicarboxylates and diarylbismuth(III) carboxylates
Publisher: CSIRO Publishing
Date: 1984
DOI: 10.1071/CH9840527
Abstract: The compounds R2BiO2CR' (R = Ph, p-MeC6H4, p-MeOC6H4, p-EtOC6H4 or C6F5 R' = Me or CF3) and RBi(O2CR')2 (R = Me, Ph, p-MeC6H4, p-MeOC6H~ or p-EtOC6H4 R' = Me or CF3) are formed on acidolysis of the corresponding triarylbismuthines in ether. The products were readily identified by 1H n.m.r. spectroscopy, even in complex mixtures, because of the successive downfield shifts of the aromatic resonances as the number of aryl groups decreases. By contrast with triarylbismuth compounds,R3-n Bi(O2CR')n (R = aryl n = 1 or 2) complexes are readily hydrolysed, whereas MeBi(O2CMe), is oxygen-sensitive but more stable to hydrolysis. The compounds undergo aryl redistribution reactions in dimethyl sulfoxide.
Nucleophilic Addition of Water and Alcohols to Dicyanonitrosomethanide: Ligands with Diverse Bonding Modes in Magnetically Coupled d‐Block Complexes
Publisher: Wiley
Date: 21-12-2009
Sulphinate complex intermediates in the Peters reaction
Publisher: Elsevier BV
Date: 1972
Hydrocarbon-soluble, polymetallic, lanthanoid aryloxides constructed utilising ligands with distal But groups
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B405717A
Organolanthanoids V. The crystal and molecular structure of DI-η5-cyclopentadienyl-1,2-dimethoxyethaneytterbium(II)
Publisher: Elsevier BV
Date: 12-1983
Novel pyrazolate coordination modes and unusual Tl · · · Tl or Tl-π-(phenyl) interactions in the crystal structures of [{Tl3(Ph2pz)3}n], [{Tl4(Ph2pz)4}n], [{Tl4(Ph2pz)3(OH)}2] and [{Tl4(MePhpz)3(OH)
Publisher: Royal Society of Chemistry (RSC)
Date: 2000
DOI: 10.1039/A909048G
Improved syntheses of Ru(CO)2 (O3SCF3)2 (bidentate) complexes and their conversion into new [Ru(CO)2 (bidentate)2]2+ complexes
Publisher: Elsevier BV
Date: 1983
Melting point suppression in new lanthanoid(iii) ionic liquids by trapping of kinetic polymorphs: An in situ synchrotron powder diffraction study
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C1CC14744G
Abstract: The complexes (N(4444))(3)[Ln(dcnm)(6)] (Ln = La-Nd, Sm N(4444) = tetrabutylammonium) display a decrease in the melting point upon fast cooling from a melt, which is shown by in situ synchrotron based X-ray powder diffraction to be due to the formation of a second, less thermodynamically stable, polymorph.
Synthesis, Ethanolysis, and Hydrolysis of Bismuth(III) ortho-Nitrobenzoate Complexes en Route to a Pearl Necklace-like Polymer of Bi10 Oxo-Clusters
Publisher: American Chemical Society (ACS)
Date: 02-07-2009
DOI: 10.1021/OM9002158
The mercuration of pentachlorobenzene: A simple route to bispentachlorophenyl-mercury
Publisher: Elsevier BV
Date: 06-1969
Potassium C–F Interactions and the Structural Consequences in N,N′-Bis(2,6-difluorophenyl)formamidinate Complexes
Publisher: MDPI AG
Date: 17-04-2017
Widely contrasting outcomes from the use of tris(pentafluorophenyl)bismuth or pentafluorophenylsilver as oxidants in the reactions of lanthanoid metals with N,N′-diarylformamidines
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0DT03044A
Abstract: Reactions of lanthanoid metals with Bi(C 6 F 5 ) 3 or AgC 6 F 5 and two widely disparate formamidines, have been investigated.
A new route to fluorocarbon-stabilized organoamidoplatinum(II) compounds—synthesis of a new isomer of [Me2)X(L)] (R = p-HC6F4 OR C6F5; X = Cl or I; L = unidentate ligand) complexes
Publisher: Elsevier BV
Date: 1989
Synthesis, structure, spectroscopic properties, and electrochemical oxidation of ruthenium(II) complexes incorporating monocarboxylate bipyridine ligands
Publisher: American Chemical Society (ACS)
Date: 20-09-2007
DOI: 10.1021/IC700796M
Abstract: [Ru(bpy)(2)(Mebpy-COOH)](PF(6))(2).3H(2)O (1), [Ru(phen)(2)(Mebpy-COOH)](ClO(4))(2).5H(2)O (2), [Ru(dppz)(2)(Mebpy-COOH)]Cl(2).9H(2)O (3), and [Ru(bpy)(dppz)(Mebpy-COOH)](PF(6))(2).5H(2)O (4) (bpy = 2,2'-bipyridine, Mebpy-COOH = 4'-methyl-2,2'-bipyridine-4-carboxylic acid, phen = 1,10-phenanthroline, dppz = dipyrido[3,2,-a ',3-c]phenazine) have been synthesized and characterized spectroscopically and by microanalysis. The [Ru(Mebpy-COOH)(CO)(2)Cl(2)].H(2)O intermediate was prepared by reaction of the monocarboxylic acid ligand, Mebpy-COOH, with [Ru(CO)(2)Cl(2)](n), and the product was then reacted with either bpy, phen, or dppz in the presence of an excess of trimethylamine-N-oxide (Me(3)NO), as the decarbonylation agent, to generate 1, 2, and 3, respectively. For compound 4, [Ru(bpy)(CO)Cl(2)](2) was reacted with Mebpy-COOH to yield [Ru(bpy)(Mebpy-COOH)(CO)Cl](PF(6)).H(2)O as a mixture of two main geometric isomers. Chemical decarbonylation in the presence of dppz gave 4 also as a mixture of two isomers. Electrochemical and spectrophotometric studies indicated that complexes 1 and 2 were present as a mixture of protonated and deprotonated forms in acetonitrile solution because of water of solvation in the isolated solid products. The X-ray crystal structure determination on crystals of [Ru(bpy)2(MebpyCOO)][Ru(bpy)(2)(MebpyCOOH)](3)(PF(6))(7), 1a, and [Ru(phen)(2)(MebpyCOO)](ClO(4)).6H(2)O, 2a, obtained from solutions of 1 and 2, respectively, revealed that 1a consisted of a mixture of protonated and deprotonated forms of the complex in a 1:3 ratio and that 2a consisted of the deprotonated derivative of 2. A distorted octahedral geometry for the Ru(II) centers was found for both complexes. Upon excitation at 450 nm, MeCN solutions of the protonated complexes 1-4 were found to exhibit emission bands in the 635-655 nm range, whereas the corresponding emission maxima of their deprotonated forms were observed at lower wavelengths. Protonation/deprotonation effects were also observed in the luminescence and electrochemical behavior of complexes 1-4. Comprehensive electrochemical studies in acetonitrile show that the ruthenium centers on 1, 2, 3, and 4 are oxidized from Ru(II) to Ru(III) with reversible potentials at 917, 929, 1052, and 1005 mV vs Fc(0/+) (Fc = ferrocene), respectively. Complexes 1 and 2 also exhibit an irreversible oxidation process in acetonitrile, and all compounds undergo ligand-based reduction processes.
Reinvestigation of a transmetallation synthesis of bis(cyclopentadienyl)samarium(II) and formation of a new soluble cyclopentadienylsamarium(II) compound
Publisher: Elsevier BV
Date: 1985
An Octanuclear Iron(III) Cluster Complex Containing the Nitroso Bridging Ligand Carbamoylcyanonitrosomethanide
Publisher: CSIRO Publishing
Date: 2009
DOI: 10.1071/CH09224
Abstract: The synthesis, structure, and magnetism is reported for an antiferromagnetically coupled, disc-shaped cluster containing the anionic ligand carbamoylcyanonitrosomethanide (ccnm), [Fe8O6(MeO)6(ccnm)6], with an FeIII8O3 core.
Reinvestigation of Reported Nucleophilic Demercurations
Publisher: Informa UK Limited
Date: 10-1983
Organoamido- and Aryloxo-lanthanoids. IV. Synthesis and X-Ray Structures of Low-Coordinate [Yb(O-2,4,6-But3C6H2)3(thf)] and [Yb(O-2,4,6-But3C6H2)2(μ-OH)(thf)]2 (thf = Tetrahydrofuran)
Publisher: CSIRO Publishing
Date: 1992
DOI: 10.1071/CH9920671
Abstract: Reaction of Yb ( Otbp )2( thf )3( tbp = 2,4,6 But3C6H2 thf = tetrahydrofuran ) with TlOtbp in tetrahydrofuran at room temperature yields thallium metal and Yb( Otbp )3( thf ) (1), which was also obtained by redox transmetallation between TlOtbp and ytterbium metal in refluxing tetrahydrofuran . Some [ Yb ( Otbp )2( �-OH) (thf)]2 (2) was also isolated from the first synthesis and is derived from hydrolysis of Yb ( Otbp )3( thf ) by traces of water. The X-ray crystal structure of (1) [triclinic, P1, a 21.78(1), b 13.89(2), c 10.461(4)� , α 109.03(5), β 99.03(3), γ 98.34(5)�, Z 2, No = 4354 'observed' data refined to R 0.0711 shows novel distorted tetrahedral four coordination for ytterbium [0-Yb-0 angles 90.6(5)-121.8(4)�, which is bonded more strongly to the aryl oxide [Yb-0 1.97(1), 2.02(1), 2.09(1) � ] than to thf [Yb-0 2.35(1) �. The X-ray structure of (2) [triclinic, P1, a 15.61(1), b 13.84(2), c 11.085(4) �, α 99.25(9),, β 94.46(4), γ 96.42(9), Z 1, No = 4718 'observed' data refined to R 0.050] indicates a centrosymmetric hydroxo -bridged dimer with a YbO2Yb core. Ytterbium has irregular five coordination with two bridging hydroxide oxygens [Yb-0 2.217(6), 2.199(6) A 0-Yb-0' 70.2(2)�, Yb-O-Yb, 109.8(3)�, non-bonding Yb…Yb 3.614(2) A], two phenoxide oxygens [2.047(7), 2.073(6) �], and a more distant thf oxygen [2.363(8) � ].
Structural Trends in Alkaline Earth and Rare Earth Metal 3,5‐Diisopropylpyrazolates
Publisher: Wiley
Date: 22-01-2007
Recurrent supramolecular scenarios within complex 3-D hydrogen bond networks derived from organic ammonium salts of (4-amino-1-hydroxybutylidine)-1,1-bisphosphonic acid
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CE01034F
Abstract: Reactions of (4-amino-1-hydroxybutylidine)-1,1-bisphosphonic acid (LH 5 ) with organic amines or diamines in aqueous solution yields crystalline compounds of the general formula [(RN)H] 2 [LH 3 ] or [(R'N)H 2 ][LH 3 ].
Kinetic stabilisation of a molecular strontium hydride complex using an extremely bulky amidinate ligand
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7CC09362D
Abstract: The first dimeric strontium hydride complex (see picture, Dip = 2,6-diisopropylphenyl, Ad = 1-adamantyl), and analogous magnesium hydride systems, have been kinetically stabilised by extremely bulky amidinate ligands, developed for this study.
Synthesis and Structures of the First Cationic Perfluoroaryllanthanoid(II ) Complexes
Publisher: Wiley
Date: 24-03-2004
Abstract: Tetraphenylborate salts of solvated pentafluorophenyllanthanoid(II) cations [Ln(C(6)F(5))(thf)(n)](+) (Ln=Eu, n=6 (1) Ln=Yb, n=5 (2)) were readily synthesized in high yield by reactions of ytterbium or europium with HgPh(C(6)F(5)) and Me(3)NHBPh(4) in THF. The structures of 1.THF and 2 confirmed the existence of well-separated ions and both 1 and 2 show notable thermal stability at room temperature. The cation in 2 was also observed in the remarkable mixed-valent complex [Yb(II)(C(6)F(5))(thf)(5)][Yb(III)(C(6)F(5))(2)[N(SiMe(3))(2)](2)] (3), fortuitously isolated in low yield from a reaction of ytterbium metal, HgPh(C(6)F(5)), and HN(SiMe(3))(2) in THF, and which additionally has an unusual bis(pentafluorophenyl)bis[bis(trimethylsilyl)amido)]ytterbate(III) anion. (171)Yb-(19)F coupling has been observed in the low-temperature (171)Yb NMR spectra of 2 and [Yb(C(6)F(5))(2)(thf)(4)].
Organothallium compounds. XIV. Thermal decomposition of some Polyfluorobenzoatobis(polyfluorophenyl)thallium(III) compounds
Publisher: CSIRO Publishing
Date: 1978
DOI: 10.1071/CH9781709
Abstract: The organothallium carboxylates, R2TIO2CR (R = C6F5, p-MeOC6F4, p-HC6F4, m-HC6F4 or o-HC6F4), prepared by reactions of appropriate halogenobis(polyfluorophenyl)thallium(III) compounds and sodium carboxylates, are considered to have associated structures with bridging carboxylate groups. Thermal decomposition of R2TlO2CR (R = C6F5, p-MeOC6F4 or p-HC6F4 or m-HC6F4) in boiling pyridine resulted in decarboxylation and formation of the corresponding tris(polyfluorophenyl)thallium compounds, which were isolated in analytically pure form as the complexes R3Tl(diox) (R = C6F5, p-HC6F4 or m-HC6F4 diox = 1,4-dioxan) and R3Tl(bpy) (R = C6F5 or p-MeOC6F4 bpy = 4,4'-bipyridyl). However, no decomposition was observed when R = o-HC6F4. The ease of decarboxylation decreased in the sequence R = C6F5 p-MeOC6F5 ≥ p-HC6F4 ≈ m-HC6F4 S o-HC6F4, and a possible mechanism is discussed. Pyrolysis of R2TIO2CR (R = C6F5, p-MeOC6F4, p-HC6F4, m-HC6F4 or o-HC6F4) at 310° under nitrogen in the absence of a solvent gave tris(polyfluorophenyl)thallium compounds (R = C6F5, p-MeOC6F4, p-HC6F4 or m-HC6F4), isolated as the dioxan complexes, thallous fluoride and polyfluorobiphenyls and polyfluoropolyphenyls. In addition, decafluorobenzophenone was obtained when R = C6F5, methyl fluoride when R = p-MeOC6F4 and the corresponding tetrafluorobenzene C6H2F4 when R = p-HC6F4, m-HC6F4 or o-HC6F4. Chlorobis(2,3,5,6-tetrafluoro-4-methoxyphenyl)thallium(III) was prepared by reaction of thallic chloride with 2,3,5,6-tetrafluoro-4-methoxyphenyllithium, which was obtained from 2,3,5,6-tetra- fluoroanisole and butyllithium.
New Approaches to 12‐Coordination: Structural Consequences of Steric Stress, Lanthanoid Contraction and Hydrogen Bonding
Publisher: Wiley
Date: 06-2010
Abstract: The anionic dinitrile ligand dicyanonitrosomethanide (dcnm), C(CN) 2 (NO) – , and the anion resulting from its addition product with water, carbamoylcyanonitrosomethanide (ccnm), C(CN)(CONH 2 )(NO) – , have been incorporated into lanthanoid complexes and display unusual η 2 (N,O) nitroso coordination modes. (Et 4 N) 3 [Ln(ccnm) 6 ] ( 1Ln 1Ln = 1La , 1Ce , 1Pr , 1Nd , 1Sm ) and (Me 4 N) 3 [Ln(ccnm) 6 ] ( 2Ln 2Ln = 2La , 2Ce , 2Pr , 2Nd ) are systems containing 12‐coordinate homoleptic trianionic lanthanoidate complexes. The nitroso groups of the ccnm ligands form three‐membered ring chelates with the lanthanoid metal centre, with the asymmetry of the nitroso η 2 interactions dependent upon the intramolecular N–H ··· O=N hydrogen bonding. Additional intermolecular hydrogen bonding interactions exist between adjacent amide and nitrile groups giving rise to 3D α‐Po and 6,8‐connected (4 12 .6 3 )(4 20 .6 8 ) networks in 1Ln and 2Ln , respectively. The compounds (Me 4 N) 3 [Ln(dcnm) 6 ] ( 3Ln 3Ln = 3La , 3Ce , 3Nd , 3Sm ) also contain a 12‐coordinate trianionic lanthanoidate complex with the nitroso group exhibiting a highly symmetrical η 2 interaction. The sterically crowded environments of [Ln(18‐crown‐6)(dcnm) 3 ] ( 4Ln 4Ln = 4La , 4Ce , 4Pr , 4Nd ) result in a shift towards a more asymmetric η 2 bonding of the nitroso group with decrease in the Ln 3+ radius. There is a corresponding increase of the Ln–O–N angle, and one ligand is η 1 (O) binding in 4Nd . The dcnm ligands in the discrete complexes [La(phen) 3 (dcnm) (3– x ) Cl x ], x ≈ 0.25 ( 5 ) (phen = 1,10‐phenanthroline), (Et 4 N)[Ce(phen) 2 (dcnm) 4 ] ( 6a / b , 6c ) and [Ce(phen) 2 (dcnm)Cl 2 H 2 O] ( 7 ) display a variety of coordination modes. Complex 5 has 1D chains formed by π–π stacking of adjacent phen co‐ligands. Complexes 6 contain the monoanionic complex [Ce(phen) 2 (dcnm) 4 ] – with two geometric isomers present in the crystal structure of 6a / b . Complex 7 forms extended 1D chains via hydrogen bonding between coordinated water and chloride atoms and an extensive array of face‐to‐face π interactions.
Synthesis and structural characterisation of the heavier alkaline earth 2,6-di-iso-propylphenolate complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0NJ00225A
N‐ Versus P‐Coordination in Bis(amino)cyclodiphosph(III)azane Complexes of Aluminum
Publisher: Wiley
Date: 29-08-2007
Abstract: The reaction of the bis(amino)cyclodiphosph(III)azane, cis-{(tBuNH)(2)(PNtBu)(2)}, with AlMe(3), AlClMe(2), AlCl(2)Me, and AlCl(3) is reported. The less Lewis acidic compound AlMe(3) forms the adduct cis-[(tBuNH)(2)(PNtBu){P.(AlMe(3))NtBu}] (1), in which the aluminum atom is exclusively coordinated to one phosphorus atom. At elevated temperatures AlMe(3) undergoes migratory exchange between the two phosphorus atoms, but no methane elimination is observed. By using the more Lewis acidic compound AlClMe(2) the P-coordinated compound cis-[(tBuNH)(2)(PNtBu){P(AlClMe(2))NtBu}] (2) can be obtained at low temperatures. Compound 2 rearranges irreversibly to a product in which the AlClMe(2) group is coordinated by one exo-cyclic nitrogen atom. A concomitant 1,2-H shift from this nitrogen atom onto the phosphorus atom is observed. The N-coordinated rearrangement product slowly decomposes via a P-N bond cleavage in solution. Reaction of the even more Lewis acidic compounds AlCl(2)Me and AlCl(3) finally led to stable adducts, cis-[(tBuNH)(PNtBu)(tBuNAlCl(2)Me){P(H)NtBu}] (3), and cis-[(tBuNH)(PNtBu)(tBuNAlCl(3)){P(H)NtBu}] (4), in which the aluminum atoms are N-coordinated by a tBuN=PH unit.
Linkage isomerism and C–H activation in an ytterbium(ii ) tetraphenylborate
Publisher: Royal Society of Chemistry (RSC)
Date: 2002
DOI: 10.1039/B208149K
Pyrolysis of mercuric bromo-4-methoxybenzoates sup3; unexpected, high yield synthesis of bis(2,5-di-bromo-4-methoxyphenyl)mercury
Publisher: Elsevier BV
Date: 08-1986
The formation of bismuth-carbon bonds by sulphur dioxide elimination
Publisher: Elsevier BV
Date: 1971
Organoamidometallics—III. 2,6-Dimethylpyridine and 1,4-dioxan as weakly coordinating polar solvents for decarboxylation syntheses of N,N-dimethyl-N′-(polyfluorophenyl)ethane-1,2-diaminato(1—)platinum(
Publisher: Elsevier BV
Date: 1989
Organothallium compounds
Publisher: Elsevier BV
Date: 06-1976
Solvent-free synthesis of bismuth thiolates and carboxylates
Publisher: Royal Society of Chemistry (RSC)
Date: 12-11-2002
DOI: 10.1039/B209347B
A simple new route to polyfluoroarylmercurials
Publisher: Elsevier BV
Date: 12-1969
Preparations and infrared spectra of some metal pentachlorobenzoates
Publisher: CSIRO Publishing
Date: 1967
DOI: 10.1071/CH9671587
Abstract: The pentachlorobenzoates, NaOCOC6Cl5,2H2O, KOCOC6Cl5,H2O, MOCOC6Cl5 (M = Cs or Tl), Hg(OCOC6Cl5)2, RHgOCOC6Cl5 (R = Ph or p-MeOC6H4), and R3SnOCOC6Cl5 (R = Ph or Me) have been prepared by neutralization, metathesis, or cleavage reactions. Vibrational assignments have been made for infrared absorption frequencies of, these compounds, pentachlorobenzoic acid, bispenta-chlorophenylmercury, and pentachlorophenylmercuric chloride. The carboxylate stretching frequencies indicate that Hg(OCOC6Cl5)2, RHgOCOC6Cl5, and R3SnOCOC6Cl5 (in chloroform) have unidentate pentachlorobenzoate ligands, whereas crystalline R3SnOCOC6Cl5 compounds have bridging pentachlorobenzoate groups. Pentachlorobenzoic acid is dimeric in the solid state, and in toluene, carbon tetrachloride, and benzene there are both monomeric and dimeric species.
Physical and Electrochemical Properties of Thioether-Functionalized Ionic Liquids
Publisher: American Chemical Society (ACS)
Date: 23-07-2009
DOI: 10.1021/JP9046769
Abstract: The preparation and characterization of a series of ionic liquids based on S-alkyl thiolonium, S-alkyl thiotetrazolium, or S-alkyl thiobenzolium cations coupled with bis(trifluoromethanesulfonyl)amide, trifluoromethanesulfonate, alkyl phosphate, chloride, and hexafluorophosphate anions are reported. All are liquid at room temperature, except the chloride salt, which has a melting point of 92 degrees C. The electrochemical characteristics of this class of ionic liquid have been determined by cyclic voltammetry. Potential windows of the ionic liquids have been obtained at glassy carbon, platinum, and gold electrodes and found to be the largest at glassy carbon, but are limited by oxidation of the thioether-functionalized cation. The voltammetry of IUPAC reference potential scale systems, ferrocene/ferrocenium, cobaltocenium/cobaltocene, and decamethylferrocene/decamethylferrocenium have been evaluated, with the last being most widely applicable. Nonadditivity of Faradaic current is found in the voltammograms of decamethylferrocene in the presence of ferrocene and cobaltocenium. Diffusion coefficient, viscosity, ionic conductivity, double layer capacitance, and other physical properties have also been measured. The dependence of the diffusion coefficient vs viscosity follows the Stokes-Einstein relationship. The properties of the ionic liquids are compared with the related imidazolium family of ionic liquids.
Organothallium compounds. VII. β-Diketonatobis(pentafluorophenyl)-thallium(III) compounds and their coordination derivatives
Publisher: CSIRO Publishing
Date: 1971
DOI: 10.1071/CH9712519
Abstract: The complexes (C6F5)2TlX [X = MeCOCHCOMe (acac), CF3COCHCOMe (tfac), CF8COCHCOCF3 (hfac), PhCOCHCOMe (bzac), PhCOCHCOPh (dbm), or quinolin-8- olate (oxinate or ox)], have been prepared by reactions between bromobis(pentafluorophenyl)thallium(III) and the appropriate sodium or thallous β-diketonates or sodium quinolin-8-olate, and react with equimolar amounts of 1,10-phenanthroline (phen) or 2,2?-bipyridyl (bipy) to give the complexes (C6F5)2- (phen or bipy)TlX (X = acac, tfac, or hfac), (C6F5)2(phen)TlX (X = bzac, dbm, or ox), but not (C6F5)2(bipy)TlX (X = bzac, dbm, or ox). On reaction with triphenyl- phosphine oxide or triphenylarsine oxide, the complexes (C6F5)2(Ph3PO or Ph3AsO)-TlX (X = acac, tfac, hfac, or dbm) and (C6F5)2Ph3AsOTl(ox) have been obtained. From conductance and molecular weight measurements and spectroscopic data, the complexes (C6F5)2TlX (except X = ox), (C6F5)2(Ph3PO or Ph3AsO)TlX, and (C6F5)2(phen or bipy)TlX, are considered to be monomeric with chelated β-diketonate or oxinate groups, and hence to contain four-, five-, and six-coordinate thallium respectively, whereas (C6F5)2Tl(ox) is considered to have an associated structure with bridging oxinate groups.
Methimazole-Based Ionic Liquids
Publisher: American Chemical Society (ACS)
Date: 11-04-2008
DOI: 10.1021/JO702511V
Abstract: The alkylation reaction of 2-mercapto-1-methylimidazole 1a with iodoethane and chlorobutane produced S-alkylmethimazole halides 2a and 2b which were subjected to anion metathesis with two different metal salts (MA) to afford methimazole-based room-temperature ionic liquids 3a, 3b, and 3c in 82%, 85%, and 87% yields, respectively. S-Alkylation giving 2a and 2b suggests that methimazole reacts through the thione tautomer.
Preparations, structures and thermal decomposition of some bis(pentafluorobenzoato)dioxouranium(VI) complexes
Publisher: Elsevier BV
Date: 1985
In vitro and in vivo studies of neutral cyclometallated complexes against murine leukæmias
Publisher: Canadian Science Publishing
Date: 06-2005
DOI: 10.1139/V05-109
Abstract: Cyclometallated µ-halogeno dimers derived from nitrogen donor ligands (1-phenylpyrazoles, 2-phenylpyridine, and 1-(2′-pyridyl)indole) were treated with unidentate nitrogen and phosphorus donor ligands to give a series of neutral monomeric palladium(II) and platinum(II) complexes. An initial prescreen of the complexes against the mouse lymphoid leukæmia cell line L1210 indicated that the complexes exhibited growth inhibitory activity over a relatively wide concentration range. Two factors that gave rise to increased activity were steric hindrance about the metal centre resulting from hindered ligands such as 2,6-dimethylpyridine, or the presence of a phosphorus donor ligand. Little correlation between palladium and platinum complexes was noted. Four complexes were selected for further in vivo study and, while none of the palladium complexes showed more than marginal activity against P388 leukæmia at doses below toxic levels, one platinum complex with a hindered metal centre did display significant antitumour activity against this model.Key words: cyclometallation, palladium, platinum, cytotoxicity, anticancer.
Organoamido‐ and Aryloxolanthanoids, 15. Organometallic Compounds of the Lanthanoids, 116. Syntheses of Low Coordination Number Divalent Lanthanoid Organoamide Complexes, and the X‐ray Crystal Structu
Publisher: Wiley
Date: 03-1997
Organothallium compounds. VIII. Arenesulphinatodiorganothallium(III) derivatives
Publisher: CSIRO Publishing
Date: 1973
DOI: 10.1071/CH9732355
Abstract: The arenesulphinatodiorganothallium(~~~) complexes R2Tl(02SR') (R = Et, Me, Ph, or C6Fj throughout R' = Ph or p-MeC6H4) have been prepared by reaction of the appropriate diorganothallium(111) halides and silver arenesulphinates, and gave the complexes Et2(phen)T1(02SR'), impure Me2(phen)T1(02SR'), Ph2(phen or bpy)Tl- (02SR'), (C6F,)2(phen, bpy, py, or Ph3PO)T1(O2SRf), and (C6Fj)2Ph3AsOT1(02SPh) on reaction with the appropriate ligands. Attempts to prepare R2(bpy)T1(02SPh) (R = Et or Me), (C6F5)2Ph3AsOT1(02S-p-MeC& ), (C6Fj)2Ph3PTl(02SPh), and Ph2(Ph3AsO)T1(02SPh) failed. The complexes Et2T1(02SRf) are dimeric with bridging 0-sulphinate groups in chloroform, and weak association of the dimeric units is con- sidered to occur in the solid state. Conclusions are more tentative for R2T1(02SRf) (R = Me, Ph, or C6F5) derivatives, since insolubility prevented molecular weight and infrared measurements in solvents of low polarity. However, associated structures with bridging bidentate 0-sulphinate groups are likely, and sulphur-oxygen stretching frequencies suggest Me2Tl(02SR') and Ph2T1(02SR') have structures similar to Et2Tl- (02SR'). The complexes R2LT1(02SR') have monomeric structures with 0-sulphinate ligands. For L = phen or bpy, the sulphinate groups are either unidentate, giving five- coordinate thallium, or bidentate, giving six-coordinate thallium, and for L = py, Ph3P0, or Ph3As0, unidentate sulphinate groups and four-coordinate thallium are likely.
Synthesis of arylbismuth(III) sulfonates from triarylbismuth compounds and arenesulfonic acids or sulfur trioxide
Publisher: Elsevier BV
Date: 03-1986
Organoamido- and aryloxo-lanthanides—VII. The x-ray structure of five-coordinate [La(OC6H6Ph2-2,6)3(THF)2]·THF
Publisher: Elsevier BV
Date: 06-1993
Organolanthanoids. XVII. The Synthesis of Bis(diphenylphosphinocyclopentadienyl)ytterbium(II) and Derived Heterobimetallic Complexes [Yb(thf)n(C5H4PPh2)2Z] [Z=Ni(CO)2, Mo(CO)4 or PtMe2; n = 1 or 2; th
Publisher: CSIRO Publishing
Date: 1992
DOI: 10.1071/CH9920567
Abstract: Reaction of diphenylphosphinocyclopentadiene with Yb (C6F5)2 or with ytterbium metal and Hg(C6F5)2 in tetrahydrofuran ( thf ) gives, after workup with toluene, the phosphinoytter-bocene , [Yb (C5H4PPh2)2( thf )]. Treatment with thf or with N,N,N′,N′- tetramethylethane-1,2-diamine ( tmen ) yields [ Yb (C5H4PPh2)2L2] (L = thf or L2 = tmen ). Redox trans- metallation between ytterbium metal and Tl (C5H4PPh2) in l,2-dimethoxyethane ( dme ) gives thallium metal and [ Yb (C5H4PPh2)2(dme )]. The ytterbium-transition metal hetero-bimetallics [ Yb ( thf ) (C2H4PPh2)2Z]. nPhMe [Z = Ni(CO)2, Mo(CO)4 or PtMe2, n = 2/3 or 1] have been prepared by reaction of [ Yb ( thf )(C5H4PPh2)2] with Ni(CO)2(PPh3)2, Mo(CO)4( nbd ) ( nbd = norbornadiene ) or PtMe2(cod) (cod = cycloocta-1,5-diene) in toluene. Treatment of the heterobimetallics with tetrahydrofuran [Z = PtMe2 or Mo(CO)4] or a preparation in thf /toluene [Z = Ni(CO)2] yields [ Yb ( thf )2(C5H4PPh2)2PtMe2]. thf, [ Yb ( thf )2(C2H4PPh2)2Mo(CO)4]. thf and [ Yb ( thf )2 (C5H4PPh2)2Ni(CO)2]. The X-ray crystal structure of the last compound (triclinic, space group Pi, a 14.514(5), b 13.565(1), c 10.866(5) 93.11(2), β 104.65(3), γ 97.25(2)�, U 2045 � 3 , Z 2, 5141 data refined to R 0.031) reveals eight-coordinate ytterbium with a pseudo-tetrahedral arrangement of two thf ligands and the cyclopentadienyl ring centroids of two ή5 -diphenylphosphinocyclopentadienide ligands . The latter are also bonded through phosphorus to the Ni(CO)2 group, resulting in tetrahedral stereochemistry for nickel. Infrared spectroscopy suggests the presence of ytterbium- isocarbonyl bonding in solid [ Yb ( thf )(C2H4PPh2)2Z] [Z = Ni(CO)2 or Mo(CO)4].
The structure of bromobis(2,3,5,6-tetrafluorophenyl) thallium(III)
Publisher: Elsevier BV
Date: 1979
Synthesis and Structural Studies of Complexes of Bis(pentafluorophenyl)mercury with Di(phosphane oxide) Ligands
Publisher: MDPI AG
Date: 20-03-2023
Abstract: The reaction of bis(pentafluorophenyl)mercury with the ligands bis(diphenylphosphano) methane P,P’-dioxide ({Ph2P(O)}2CH2) (1), bis{2-(N,N,N’N’-tetraethyldiaminophosphano) imidazol-1-yl} methane P,P’-dioxide ({2-PO(NEt2)2C3N2H2}2CH2) (2) and bis (2-diphenylphosphanophenyl) ether P,P’-dioxide ({2-PPh2(O)C6H4}2O) (3) afforded crystalline σ-donor complexes [{Hg(C6F5)2}2{Ph2P(O)}2CH2] (1Hg), [Hg(C6F5)2{2-PO(NEt2)2C3N2H2}2CH2]n (2Hg) and [Hg(C6F5)2{2-PPh2(O)C6H4}2O] (3Hg), respectively. The molecular structures of 1Hg, 2Hg and 3Hg show considerable differences. In complex 1Hg, a single bridging bidentate ligand connects two three-coordinate T-shape mercury atoms with a near linear C-Hg-C atom array. Complex 2Hg is a one-dimensional coordination polymer in which adjacent four-coordinate mercury atoms with a linear C-Hg-C atom array are linked by bridging bidentate O,O’- ligands, whilst in complex 3Hg a T-shape three-coordinate mercury atom is ligated by (3) in a monodentate fashion. The Hg-O bond lengths of complexes 1Hg, 2Hg and 3Hg differ substantially (range 2.5373(14)-2.966(3) Å) owing to structural and bonding differences.
Coordination Polymers of Small Cyano Anions
Publisher: Swiss Chemical Society
Date: 26-06-2013
Abstract: Small cyano anions, and their derivatives, have proved to be remarkably versatile building blocks for coordination polymers. They have led to magnetically ordered materials, structures with new entangled motifs or novel topologies, and a significant structural ersity, including polymorphism, induced by subtle changes in anion, cation, co-ligands, preparative conditions, or even desolvation.
Divalent Tetra- and Penta-phenylcyclopentadienyl Europium and Samarium Sandwich and Half-Sandwich Complexes: Synthesis, Characterization, and Remarkable Luminescence Properties
Publisher: American Chemical Society (ACS)
Date: 25-11-2015
The assessment of some cobalt and cobalt-tellurium complexes for MOCVD applications
Publisher: No publisher found
Date: 1996
A preparative distinction between the donor properties of 1,10-phenanthroline and 2,2′-bipyridyl
Publisher: Elsevier BV
Date: 10-1966
Organomercury Compounds
Publisher: Elsevier BV
Date: 08-1978
The chemistry of organothallium compounds. Part III. Far-infrared spectra of halogenobis(pentafluorophenyl)thallium(III) compounds
Publisher: Royal Society of Chemistry (RSC)
Date: 1967
DOI: 10.1039/J19670000158
Organoamido- and Aryloxo-lanthanoids. III. Preparation and X-Ray Structure of Bis(μ-3,5-dimethylpyrazolato-N:N′)bis(μ-tetrahydrofuran-O)-bis[bis(η2-3,5-dimethylpyrazolato-N,N')neodymium(III)]
Publisher: CSIRO Publishing
Date: 1991
DOI: 10.1071/CH9910613
Abstract: Reaction of neodymium metal with bis ( pentafluorophenyl )mercury and pyrazole ( Hpz ) or 3,5-dimethylpyrazole ( Hdmpz ) in tetrahydrofuran ( thf ) yields Nd ( pz )3 or [ Nd ( dmpz )3( thf )]2. X-Ray crystallography has shown that [Nd (dmpz )3( thf )]2 [triclinic, space group Pī (No. 2), a 11.070(4), b 11.364(3), c 10.867(2)Ǻ, α 103.00(1), β 120.78(3), γ 97.68(2)°, R 0.0235, Rw 0.0247 for 5575 observed reflections] has a novel centrosymmetric dimeric structure. Each neodymium is eight-coordinate (4,4 bicapped trigonal prism) with two terminal chelating dmpz ligands [ Nd -N 2.400(2), 2.413(3), 2.422(3), 2.426(3)Ǻ], two bridging dmpz ligands [ Nd -N 2.509(2), 2.511(2)Ǻ], and, unexpectedly, two bridging tetrahydrofuran ligands [ Nd -O 2.792(2), 2.757(2)Ǻ].
Reactions of diorganoytterbium compounds with ketones and aldehydes
Publisher: Elsevier BV
Date: 1981
Structural and solution studies of phenylbismuth(III) sulfonate complexes and their activity against Helicobacter pylori
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0DT00629G
Abstract: Three bis-phenylbismuth sulfonates [Ph(2)Bi(O(3)SR)](∞) (R = p-tolyl 1, mesityl 2 or S-(+)-10-c horyl 3) have been synthesised and characterised. Their tendency for ligand redistribution in solution, and activity against the bacterium Helicobacter pylori have been investigated. The structures of 2 and 3 have been authenticated by X-ray diffraction crystallography. They are structurally very similar with polymeric helical chain structures composed of four coordinate Bi atoms which bridge between two sulfonate O atoms with near linear O-Bi-O bond angles. The two phenyl rings are cis to one another and trans to the stereochemically active lone pair. Upon dissolution of the pure compounds 1, 2 and 3, a ligand redistribution reaction occurs in which the mono-phenylbismuth bis-sulfonates, the bismuth tris-sulfonates and triphenylbismuth are formed. Two further complexes of general formula [PhBi(O(3)SR)(2)](∞) (where R = p-tolyl 4, and mesityl 5) were thus obtained and their crystal structures determined. The presence of the single sulfonato ligand in compounds 1, 2 and 3 resulted in a dramatic increase in bacteriocidial activity towards H. pylori (MIC values of ≥6.25 μg mL(-1)) relative to BiPh(3) (>64 μg mL(-1)) and the sulfonic acids, which were essentially inactive.
Organoindium compounds. I. Preparative routes to pentafluorophenylindium compounds
Publisher: CSIRO Publishing
Date: 1971
DOI: 10.1071/CH9711771
Abstract: Trispentafluorophenylindium has been prepared by heating iodopentafluoro-benzene with an excess of indium metal, but was obtained mixed with iodobispenta-fluorophenylindium when the stoicheiometric amount was used. An attempted synthesis by thermal decomposition of indium trispentafluorobenzoate was un-successful. Reaction of indium with bispentafluorophenylmercury and subsequent treatment with ether gave (C6F5)3In,OEt2. The complex (C6F5)3In,diox (diox = 1,4-dioxan) has been obtained by reaction of indium trichloride with pentafluorophenyl-magnesium chloride or with an excess of bispentafluorophenylmagnesium, and C6F5InCl2,diox from bispentafluorophenylmagnesium and an excess of indium trichloride.
Coordination Polymers of Increasing Complexity Derived from Alkali Metal Cations and (4-Amino-1-hydroxybutylidine)-1,1-bisphosphonic Acid (Alendronic Acid): The Competitive Influences of Coordination
Publisher: American Chemical Society (ACS)
Date: 24-08-2015
Conditions Favoring the Formation of Monomeric PtIIIDerivatives in the Electrochemical Oxidation oftrans-[PtII{(p-BrC6F4)NCH2CH
Publisher:
Wiley
Date:
21-04-2015
Publisher: Wiley
Date: 21-04-2015
A Striking, Multifaceted, Decalithium Aggregate with Carbanion, Organoamide, and Alkoxide Functionalities
Publisher: Wiley
Date: 06-2001
DOI: 10.1002/1521-3773(20010601)40:11<2108::AID-ANIE2108>3.0.CO;2-C
Syntheses of Bis(aryloxo)halogenoytterbium(III) Complexes: [Yb(OAr)2X(THF)2] (X = Cl, Br, I; OAr = OC6H2-2,6-tBu2-4-R; R = H, Me,tBu) and the X-Ray Crystal Structures of [Yb(OC6H2-2,6-tBu2-4-Me)2I(THF
Publisher: Wiley
Date: 07-2001
DOI: 10.1002/1521-3749(200107)627:7<1652::AID-ZAAC1652>3.0.CO;2-7
Pyrazolate Coordination Continues To Amaze���The New��-��2:��1Binding Mode and the First Case of Unidentate Coordination to a Rare Earth Metal
Publisher: Wiley
Date: 02-09-2002
DOI: 10.1002/1521-3773(20020902)41:17<3249::AID-ANIE3249>3.0.CO;2-D
The X-ray crystal structure of Hg(p-MeC6H4)(O2CC6F5) from synchrotron radiation
Publisher: Springer Science and Business Media LLC
Date: 07-2004
Expanding the Series of [RE2Ca(OQ)8] Structures: New Heterobimetallic Rare Earth/Alkaline Earth 8‐Quinolinolate Complexes
Publisher: Wiley
Date: 19-07-2012
Abstract: Abstract. A series of heterobimetallic complexes [RE 2 Ca(OQ) 8 ] · n HOQ(RE = Sm, Gd, Tb, Ho, Tm, Yb, Lu, Y, Sc) and the isostructural [Gd 2 Mg(OQ) 8 ] were synthesised and structurally characterised. They were mainly obtained after direct reactions of the elemental rare earth metals with calcium metal in the presence of 8‐hydroxyquinoline (HOQ) and a 1, 3, 5‐tri‐ tert ‐butyl‐benzene ( t BuB) flux, and some complexes were synthesised by pseudo solid‐state rearrangement reactions between powdered RE(OQ) 3 and AE(OQ) 2 (AE = Mg, Ca) in a 1, 2, 4, 5‐tetramethylbenzene (TMB) flux, at elevated temperatures. The linear trinuclear [RE 2 Ca(OQ) 8 ] moieties show a six‐coordinate central calcium atom flanked by two eight‐coordinate rare earth atoms surrounded by six chelating‐bridging OQ and two terminal chelating OQ ligands. The structurally novel [Sc 2 Ca(OQ) 8 ] has a bent Sc‐Ca‐Sc backbone and exhibits an eight‐coordinate central calcium and two seven‐coordinate scandium ions.
The use of Resonant X-ray Emission Spectroscopy (RXES) for the electronic analysis of metal complexes and their interactions with biomolecules
Publisher: Elsevier BV
Date: 09-2015
DOI: 10.1016/J.DDTEC.2015.07.001
Abstract: This review presents a new application of Resonant X-ray Emission Spectroscopy (RXES) to study the mechanism of action of metal containing anticancer derivatives and in particular platinum in situ and in vivo. The technique is an ex le of a photon-in photon-out X-ray spectroscopic approach, which enables chemical speciation of drugs to be determined and therefore to derive action mechanisms, and to determine drug binding rates under physiological conditions and therapeutic concentrations. This is made feasible due to the atomic specificity and high penetration depth of RXES. The review presents ex les of the three main types of information that can be obtained by RXES and establishes an experimental protocol to perfect the measurements within cells.
The Synthesis by Decarboxylation Reactions and Crystal Structures of 1, n–Bis(diphenylphosphino)alkane(pentafluorophenyl)‐platinum(II) Complexes
Publisher: Wiley
Date: 23-03-2005
Synthesis and Characterisation of Thiophene‐Functionalised Lanthanoid Diketonate Clusters with Solvent‐Modulated Europium Luminescence
Publisher: Wiley
Date: 06-2012
Transformation of a 1D to 3D coordination polymer mediated by low temperature lattice solvent loss
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0CC00711K
Abstract: The desolvation of lattice methanol from between the 1D chains in {[Cu(4,4'-bipyridine)(ccnm)(2)].4MeOH} (ccnm = carbamoylcyanonitrosomethanide) under ambient conditions, a weight loss of 22.4%, results in a solid state conversion to the 3D network [Cu(4,4'-bipyridine)(ccnm)(2)].
Refutation of the synthesis of tetrakis(cyclopentadienyl)cerium(IV)
Publisher: Elsevier BV
Date: 1983
Platinum Diolefin Complexes – Synthesis, Structures, and Cytotoxicity
Publisher: Wiley
Date: 24-11-2014
A novel desulphination path to tris(polyfluorophenyl)thallium(III) compounds
Publisher: Elsevier BV
Date: 05-1979
Organomercury Derivatives of Dibenzoylmethane
Publisher: Elsevier BV
Date: 03-1974
The vibrational spectra of some phenylmercuric halides and diphenylmercury
Publisher: CSIRO Publishing
Date: 1977
DOI: 10.1071/CH9771905
Abstract: The Raman spectra of phenylmercuric chloride, phenylmercuric bromide, phenylmercuric iodide and diphenylmercury, and the infrared and Raman spectra of diphenylmercury in solution are reported. Using the previously reported infrared spectra of these compounds, vibrations were assigned, normal coordinate analyses were performed and frequencies were calculated using a valence force field. Good agreement was achieved between observed and calculated frequencies. The structure of diphenyl-mercury in solution is discussed.
Organomercury compounds. IV. Infrared spectra, structures, and thermal decomposition of mercuric arylsulphinates
Publisher: CSIRO Publishing
Date: 1967
DOI: 10.1071/CH9671367
Abstract: The structures of mercuric benzenesulphinate and p-toluenesulphinate have been investigated by infrared spectroscopy, and it has been shown that the arylsulphinate ions are coordinated to mercury through sulphur and not through oxygen. Thermal decomposition of the benzenesulphinate, at the melting point or in toluene, gives good yields of diphenylmercury. No di-p-tolylmercury is obtained from pyrolysis of the p-toluenesulphinate in absence of a solvent, but a moderate yield is obtained when the compound is decomposed in boiling toluene.
Organothallium compounds XIII. Dithallation of some monocyclic aromatic compounds
Publisher: Elsevier BV
Date: 1978
Synthesis and characterisation of divalent di(1,3‐bis(diphenylphosphano)cyclopentadienyl)lanthanoid and alkaline earth complexes as potential platforms for heterometallic complexes
Publisher: Wiley
Date: 07-10-2022
Abstract: New alent lanthanoid and alkaline earth metal complexes bearing the 1,3‐bis(diphenylphosphano)cyclopentadienyl ligand have been synthesised using the redox‐transmetallation protolysis (RTP) approach. From the reaction of the corresponding metal, diphenylmercury and the proligand C 5 H 4 (PPh 2 ) 2 , the compounds [M(η 5 ‐C 5 H 3 (PPh 2 ) 2 ‐1,3) 2 (S)] (with M=Yb, S=(thf) 2 or M=Yb, Eu, Ca, Sr, Ba, S=dme) were isolated and characterised by X‐ray diffraction and multinuclear NMR spectroscopy. These compounds may provide a platform for early‐late heterobimetallic complexes.
A Novel Alkene(alkyl)(aqua)(aryl)platinum(II) Complex - [Pt{CH(CH2C6F5)CH2CH2CH=CH2}(C6F5)(OH2)]
Publisher: Wiley
Date: 05-2001
DOI: 10.1002/1521-3749(200105)627:5<811::AID-ZAAC811>3.0.CO;2-A
Tetramethylammonium hexanitratoneodymiate(III). Structural variations of the [Nd(NO3)6]3− anion in a single crystal
Publisher: Informa UK Limited
Date: 10-09-2007
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