ORCID Profile
0000-0002-2169-2718
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Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9CC06272F
Abstract: The only reported synthesis of a [ n ]-azacubane, 1,4-diazacubane, on re-examination revealed a disordered piperazine that constitutes the previously reported Ni 2+ Kagome metal organic framework (MOF).
Publisher: CSIRO Publishing
Date: 2020
DOI: 10.1071/CH19468
Abstract: The synthesis of the extended dipyridyl ligand 4,4′-(2,5-dimethyl-1,4-phenylene)dipyridine (L) in an improved yield via the palladium catalysed Suzuki coupling of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (1) and 1,4-dibromo-2,5-dimethylbenzene (2) is reported along with its use to form a two-dimensional coordination polymer [Co2L2(OAc)4(H2O)2]n. The coordination polymer consists of one-dimensional chains of octahedral cobalt ions bridged by acetate ligands which are connected to form two dimensional sheets with square lattice (sql) topology via the dipyridyl ligands (L). The structure contains small voids totalling ~6.6% of the unit cell volume. The crystal structures 1, L, L·2H2O, and L·2HNO3 are also reported.
Publisher: American Chemical Society (ACS)
Date: 30-11-2016
DOI: 10.1021/ACS.INORGCHEM.6B02007
Abstract: A series of enantiopure ruthenium(II) polypyridyl complexes are reported that feature pendant pyridyl groups suitable for building larger self-assembled structures. The complexes are characterized in detail in solution using NMR spectroscopy, cyclic voltammetry, and photophysical methods and in the solid state using single-crystal X-ray crystallography. The complexes are luminescent, displaying long excited-state lifetimes that are quenched when the pendant pyridyl groups are protonated. Reaction with cadmium(II) ions results in the formation of a mixed-metal one-dimensional coordination polymer, which was characterized by single-crystal X-ray crystallography.
Publisher: American Chemical Society (ACS)
Date: 03-07-2018
DOI: 10.1021/ACS.INORGCHEM.8B01157
Abstract: We have designed linear metalloligands which contain a central photoactive [Ru(N
Publisher: American Chemical Society (ACS)
Date: 31-07-2014
DOI: 10.1021/IC5014768
Abstract: A group of sterically encumbered peri-substituted acenaphthenes have been prepared, containing tin moieties at the 5,6-positions in 1-3 ([Acenap(SnR3)2], Acenap = acenaphthene-5,6-diyl R3 = Ph3 (1), Me3 (2) [(Acenap)2(SnMe2)2] (3)) and phosphorus functional groups at the proximal peri-positions in 4 and 5 ([Acenap(PR2)(P(i)Pr2)] R2 = Ph2 (4), Ph((i)Pr) (5)). Bis(stannane) structures 1-3 are dominated by repulsive interactions between the bulky tin groups, leading to peri-distances approaching the sum of van der Waals radii. Conversely, the quasi-linear CPh-P···P three-body fragments found in bis(phosphine) 4 suggest the presence of a lp(P)-σ*(P-C) donor-acceptor 3c-4e type interaction, supported by a notably short intramolecular P···P distance and notably large JPP through-space coupling (180 Hz). Severely strained bis(sulfides) 4-S and 5-S, experiencing pronounced in-plane and out-of-plane displacements of the exocyclic peri-bonds, have also been isolated following treatment of 4 and 5 with sulfur. The resulting nonbonded intramolecular P···P distances, ∼4.05 Å and ∼12% longer than twice the van der Waals radii of P (3.60 Å), are among the largest ever reported peri-separations, independent of the heteroatoms involved, and comparable to the distance found in 1 containing the larger Sn atoms (4.07 Å). In addition we report two metal complexes with square planar [(4)PtCl2] (4-Pt) and octahedral cis-[(4)Mo(CO)4] (4-Mo) geometries. In both complexes the bis(phosphine) backbone is distorted, but notably less so than in bis(sulfide) 4-S. All compounds were fully characterized, and except for bis(phosphine) 5, crystal structures were determined.
Publisher: Wiley
Date: 27-03-2015
Abstract: A series of phosphine-stibine and phosphine-stiborane peri-substituted acenaphthenes containing all permutations of pentavalent groups -SbCln Ph4-n (5-9), as well as trivalent groups -SbCl2 , -Sb(R)Cl, and -SbPh2 (2-4, R=Ph, Mes), were synthesised and fully characterised by single crystal diffraction and multinuclear NMR spectroscopy. In addition, the bonding in these species was studied by DFT computational methods. The P-Sb dative interactions in both series range from strongly bonding to non-bonding as the Lewis acidity of the Sb acceptor is decreased. In the pentavalent antimony series, a significant change in the P-Sb distance is observed between -SbClPh3 and -SbCl2 Ph2 derivatives 6 and 7, respectively, consistent with a change from a bonding to a non-bonding interaction in response to relatively small modification in Lewis acidity of the acceptor. In the Sb(III) series, two geometric forms are observed. The P-Sb bond length in the SbCl2 derivative 2 is as expected for a normal (rather than a dative) bond. Rather unexpectedly, the phosphine-stiborane complexes 5-9 represent the first ex les of the σ(4) P→σ(6) Sb structural motif.
Publisher: Wiley
Date: 16-12-2013
Abstract: A new structural arrangement Te3 (RP(III) )3 and the first crystal structures of organophosphorus(III)-tellurium heterocycles are presented. The heterocycles can be stabilized and structurally characterized by the appropriate choice of substituents in Tem (P(III) R)n (m=1: n=2, R=OMes* (Mes*=supermesityl or 2,4,6-tri-tert-butylphenyl) n=3, R=adamantyl (Ad) n=4, R=ferrocene (Fc) m=n=3: R=trityl (Trt), Mesor by the installation of a P(V) 2 N2 anchor in RP(III) [TeP(V) (tBuN)(μ-NtBu)]2 (R=Ad, tBu).
Publisher: Wiley
Date: 30-10-2015
Abstract: The ionothermal synthesis, structure, and magnetic susceptibility of a novel inorganic–organic hybrid material, imidazolium vanadium(III,IV) oxyfluoride [C 3 H 5 N 2 ][V 9 O 6 F 24 (H 2 O) 2 ] (ImVOF) are presented. The structure consists of inorganic vanadium oxyfluoride slabs with kagome layers of V 4+ S = ions separated by a mixed valence layer. These inorganic slabs are intercalated with imidazolium cations. Quinuclidinium (Q) and pyrazinium (Pyz) cations can also be incorporated into the hybrid structure type to give QVOF and PyzVOF analogues, respectively. The highly frustrated topology of the inorganic slabs, along with the quantum nature of the magnetism associated with V 4+ , means that these materials are excellent candidates to host exotic magnetic ground states, such as the highly sought quantum spin liquid. Magnetic susceptibility measurements of all s les suggest an absence of conventional long‐range magnetic order down to 2 K despite considerable antiferromagnetic exchange.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4CC01073F
Abstract: Reaction of Woollins' reagent ( WR ) with pyridine yields the P(V) species PhPSe 2 stabilised by pyridine coordination. Its potential as a selenation reagent under mild conditions was shown by calculations and an experimental comparison to WR .
Publisher: Informa UK Limited
Date: 03-03-2016
Publisher: American Chemical Society (ACS)
Date: 24-09-2012
DOI: 10.1021/IC301627Y
Abstract: Twelve related monocation chalconium salts [{Nap(EPh)(E'Ph)Me}(+){CF(3)SO(3)}(-)] 2-4, [{Acenap(Br)(EPh)Me}{CF(3)SO(3)}(-)] 5-7, and [{Acenap(EPh)(E'Ph)Me}(+){CF(3)SO(3)}(-)] 8-13 have been prepared and structurally characterized. For their synthesis naphthalene compounds [Nap(EPh)(E'Ph)] (Nap = naphthalene-1,8-diyl E/E' = S, Se, Te) N2-N4 and associated acenaphthene derivatives [Acenap(X)(EPh)]/[Acenap(EPh)(E'Ph)] (Acenap = acenaphthene-5,6-diyl E/E' = S, Se, Te X = Br) A5-A13 were independently treated with a single molar equivalent of methyl trifluoromethanesulfonate (MeOTf). In addition, reaction of bis-tellurium compound A10 with 2 equiv of MeOTf afforded the doubly methylated dication salt [{Acenap(TePhMe)(2)}(2+){(CF(3)SO(3))(2)}(2-)}] 14. The distortion of the rigid naphthalene and acenaphthene backbone away from ideal was investigated in each case and correlated in general with the steric bulk of the interacting atoms located at the proximal peri positions. Naturally, introduction of the ethane linker in acenaphthene compounds increased the splay of the bay region compared with equivalent naphthalene derivatives resulting in greater peri distances. The conformation of the aromatic rings and subsequent location of p-type lone pairs has a significant impact on the geometry of the peri region, with anomalies in peri separations correlated to the ability of the frontier orbitals to take part in attractive or repulsive interactions. In all but one of the monocations a quasi-linear three-body C(Me)-E···Z (E = Te, Se, S Z = Br/E) fragment provides an attractive component for the E···Z interaction. Density functional studies confirmed these interactions and suggested the onset of formation of three-center, four-electron bonding under appropriate geometric conditions, becoming more prevalent as heavier congeners are introduced along the series. The increasingly large J values for Se-Se, Te-Se, and Te-Te coupling observed in the (77)Se and (125)Te NMR spectra for 1, 3, 4, 9, 10, and 13 give further evidence for the existence of a weakly attractive through-space interaction.
Publisher: Wiley
Date: 24-02-2014
Publisher: American Chemical Society (ACS)
Date: 05-03-2012
DOI: 10.1021/OM201253T
Publisher: Georg Thieme Verlag KG
Date: 03-02-2015
Publisher: American Chemical Society (ACS)
Date: 09-06-2014
DOI: 10.1021/IC500697M
Abstract: The reactions of peri-substitution-stabilized phosphanylidene-phosphorane 1 with [AuCl(tht)] or [PtCl2(cod)] afford binuclear complexes [((1)(AuCl)2)2] 2 and [((1)(PtCl2))2] 3, in which four electrons of the ligand are used in bonding to two metal atoms in the bridging arrangement. Reactions of 1 with [Mo(CO)4(nbd)] or (RhCl2Cp*)2 afford mononuclear complexes [(1)2Mo(CO)4] 4 and [(1)RhCl2Cp*] 5, in which two electrons of the ligand are used to form terminal complexes. Formation of these complexes disrupts the negative hyperconjugation at the P-P bond to various extents, which is mirrored by variations in their P-P bond distances (2.179(4)-2.246(4) Å). The P-P bond is ruptured upon formation of Pd diphosphene complex 6, which is likely to proceed through a phosphinidene intermediate. In air, 1 is fully oxidized to phosphonic acid 7. Reactions of 1 with chalcogens under mild conditions generally afford mixtures of products, from which the trithionated 8, dithionated 9, diselenated 10, and monotellurated 11 species were isolated. The bonding in the chalcogeno derivatives is discussed using DFT (B3LYP) and natural bond orbital analysis, which indicate a contribution from dative bonding in 8-10. The buttressing effect of the peri backbone is shown to be an essential factor in the formation of the single push-double-pull bis(borane) 13. This is demonstrated experimentally through a synthesis parallel to that used to make 13, but lacking the backbone, which leads to different products. The P-P bond distances in the reported products, as well as additional species, are correlated with Wiberg bond indices, showing very good agreement for a variety of bonding modes, including the negative hyperconjugation.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5RA27594F
Abstract: The fundamental synthetic building blocks FcPH 2 and FcPCl 2 are obtained in high yield and excellent purities via the fully regiospecific electrophilic monofunctionalisation of ferrocene with P 4 S 10 , thus replacing inconvenient t BuLi based procedures.
Publisher: American Chemical Society (ACS)
Date: 02-10-2014
DOI: 10.1021/OM500755W
Publisher: Wiley
Date: 12-10-2015
Abstract: The synthesis and characterization of abnormal N‐heterocyclic carbene, cyclic (alkyl)(amino)carbene, and mesoionic carbene copper(I) complexes are reported. These organometallic species are obtained via a versatile and inexpensive synthetic pathway using readily available reactants, namely copper oxide and iminium salts. The catalytic activity of this series of complexes was evaluated in the [3+2] cycloaddition of alkynes with azides (CuAAC). Outstanding catalytic properties were observed for the abnormal NHC‐ and triazolylidene‐based copper(I) complexes. magnified image
Publisher: Wiley
Date: 24-09-2013
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1CC01567B
Abstract: PhICl 2 reacts with pyridine to form a simple coordination complex via halogen bonding and does not result in an activated [PhI(Pyr)(Cl)] + cation as previously proposed.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5DT02542G
Abstract: Subtle changes in the structure of the backbone can lead to profound differences in the binding modes of dithiolato ligands in rhodium and iridium half sandwich complexes.
Publisher: American Chemical Society (ACS)
Date: 26-02-2015
DOI: 10.1021/ACS.INORGCHEM.5B00161
Abstract: A comprehensive investigation of reactions of alkali-metal derivatives of the ditelluro dianion [TePV(NtBu)(μ-NtBu)]22– (L2–, E = Te) with p-block element halides produced a series of novel heterocycles incorporating P2VN2 rings, tellurium, and group 13–16 elements. The dianion engages in Te,Te′-chelation to the metal center in Ph2Ge and R2Sn (R = tBu, nBu, Ph) derivatives similar behavior was noted for group 14 derivatives of L2– (E = S, Se). In the case of group 13 trihalides MCl3 (M = Ga, In), neutral spirocyclic complexes (L)M[NtBu(Te)PV(μ-NtBu)2PIIIN(H)tBu)] (M = Ga, In) comprised of a Te,Te′-chelated ligand L2– and a N,Te-bonded ligand resulting from loss of Te and monoprotonation were obtained. In reactions with RPCl2 (R = tBu, Ad, iPr2N) a significant difference was observed between Se- and S-containing systems. In the former case, Se,Se′-chelated derivatives were formed in high yields, whereas the N,S-chelated isomers predominated for sulfur. All complexes were characterized by multinuclear (1H, 31P, 77Se, 119Sn, and 125Te) NMR spectroscopy this technique was especially useful in the analysis of the mixture of (L)(Se) and (L)(SeSe) obtained from the reaction of Se2Cl2 with L2– (E = Te). Single-crystal X-ray structures were obtained for the spirocyclic In complex (9), (L)GePh2 (E = Te, 10), (L)SntBu2 (E = Te, 12a) E = Se, 12aSe, E = S, 12aS) and (L)(μ-SeSe) (E = Te, 16).
Publisher: CSIRO Publishing
Date: 2017
DOI: 10.1071/CH16620
Abstract: Four heteroleptic ruthenium(ii) complexes of 4′-functionalised 2,2′:6′,2′′-terpyridine are reported, along with their solid-state single-crystal X-ray structures. The complexes feature complementary hydrogen-bond donor (phenol) and acceptor (pyridyl) groups designed to assemble into one-dimensional polymers. In one ex le, the system obeys the programmed instructions to form a one-dimensional, self-complementary hydrogen-bonded polymer. In one other ex le, a water-bridged hydrogen-bonded polymer is formed. In the remaining two structures, aryl–aryl interactions dominate the intermolecular interactions, and outweigh the contribution of intermolecular hydrogen bonding.
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2DT32716C
Abstract: Oxidation of alkali metal derivatives of [Te((t)BuN)P(μ-N(t)Bu)(2)P(N(t)Bu)Te](2-) with I(2) produces the intermediate ditelluride dianion [Te((t)BuN)P(μ-N(t)Bu)(2)P(N(t)Bu)Te](2)(2-) with a planar PTeTeP conformation and, subsequently, the cyclic tritelluride [((t)BuN)P(μ-N(t)Bu)(2)P(N(t)Bu)(μ-TeTeTe)].
Publisher: American Chemical Society (ACS)
Date: 18-02-2015
DOI: 10.1021/IC503056Z
Abstract: A series of peri-substituted phosphorus-tellurium systems R'Te-Acenap-PR2 (R' = Ph, p-An, Nap, Mes, Tip Acenap = acenaphthene-5,6-diyl (-C12H8) R = (i)Pr, Ph) exhibiting large "through-space" spin-spin coupling constants and the "onset" of three-center four-electron type interactions is presented. The influence of the substituents at the phosphorus and tellurium atoms as well as their behavior upon oxidation (with S, Se) or metal-coordination (Pt, Au) is discussed using NMR spectroscopy, single-crystal X-ray diffraction, and advanced density functional theory studies including NBO, AIM, and ELI-D analyses.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT12031C
Abstract: Sterically crowded peri-substituted selenium and tellurium acenaphthene donors D1-D7 [Acenap(EPh)(Br) E = Se, Te Acenap(SePh)(EPh) E = Se, S Acenap(TePh)(EPh) E = S, Se, Te] react with dibromine and diiodine acceptors to afford a group of structurally erse addition products 1-12, comparable in some cases to previously reported naphthalene analogues. Tellurium donors D4-D6 react conventionally with the dihalogens to afford insertion adducts 6-11 (X-R(2)Te-X) exhibiting molecular see-saw geometries, characterised by hypervalent X-Te-X quasi-linear fragments. The reactions of selenium donors D1-D3 with diiodine afford expected neutral charge-transfer (CT) spoke adducts 1, 4 and 5 (R(2)Se-I-I) containing quasi-linear Se-I-I alignments. Conversely, treatment of D2 and D3 with dibromine results in the formation of two tribromide salts 2 and 3 containing bromoselanyl cations [R(2)Se-Br](+)···[Br-Br(2)](-), each exhibiting a quasi-linear three-body Br-Se···E (E = Se, S) fragment. The peri-bonding in these species can be thought of as a weak hypervalent G···Se-X three-centre, four-electron (3c-4e) type interaction, closely related to the T-shaped 3c-4e interaction. Density-functional calculations performed on 2 and 3 and their bare cations (2a and 3a) reveal Wiberg bond indices of 0.25-0.37, suggesting substantial 3c-4e character in these systems. The presence of such an interaction operating in 2 and 3 alleviates steric strain within the peri-region and minimises the degree of molecular distortion required to achieve a relaxed geometry. Ditellurium donor D7 reacts with dibromine to afford an unorthodox insertion adduct 12 containing a Te-O-Te bridge and two quasi-linear Br-Te-O fragments, with the central tellurium atoms assuming a molecular see-saw geometry. Whilst DFT calculations indicate 12 is thermodynamically unfavourable, its formation is viable under experimental conditions.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4DT03257H
Abstract: The versatile coordinating ability of a novel spirocyclic, P 2 N 2 -supported Te 5 dianion is exemplified by N , N ′-bonding to Na + ions and Te,Te′,Te′′ linkages to a Cp*Rh( iii ) group.
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0CE00176G
Abstract: A new parameter is proposed to quantify the linearity of halogen bonds.
Publisher: American Chemical Society (ACS)
Date: 08-05-2014
DOI: 10.1021/OM500289B
Publisher: American Chemical Society (ACS)
Date: 27-03-2013
DOI: 10.1021/IC3024875
Abstract: Coupling of two acenaphthene backbones through a phosphorus atom in a geminal fashion gives the first geminally bis(peri-substituted) tridentate phosphine 1. The rigid nature of the aromatic backbone and overall crowding of the molecule result in a rather inflexible ligand, with the three phosphorus atoms forming a relatively compact triangular cluster. Phosphine 1 displays restricted dynamics on an NMR time scale, which leads to the anisochronicity of all three phosphorus nuclei at low temperatures. Strained bis- and tris(sulfides) 2 and 3 and the bis(selenide) 4 have been isolated from the reaction of 1 with sulfur and selenium, respectively. These chalcogeno derivatives display pronounced in-plane and out-of-plane distortions of the aromatic backbones, indicating the limits of their angular distortions. In addition, we report metal complexes with tetrahedral [(1)Cu(MeCN)][BF4] (5), square planar [(1)PtCl][Cl] (6), trigonal bipyramidal [(1)FeCl2] (7), and octahedral fac-[(1)Mo(CO)3] (8) geometries. In all of these complexes the tris(phosphine) backbone is distorted, however to a significantly smaller extent than that in the mentioned chalcogenides 2-4. Complexes 5 and 8 show fluxionality in (31)P and (1)H NMR. All new compounds 1-8 were fully characterized, and their crystal structures are reported. Conclusions from dynamic NMR observations were augmented by DFT calculations.
Publisher: Wiley
Date: 10-01-2014
Publisher: American Chemical Society (ACS)
Date: 05-05-2015
DOI: 10.1021/JACS.5B03353
Abstract: Solid-state NMR spectra of new P-Se heterocycles based on peri-substituted naphthalene motifs show the presence of unusual J couplings between Se and P. These couplings are between atoms in adjacent molecules and occur "through space", rather than through conventional covalent bonds. Experimental measurements are supported by relativistic DFT calculations, which confirm the presence of couplings between nonbonded atoms, and provide information on the pathway of the interaction. This observation improves the understanding of J couplings and offers insight into the factors that affect crystal packing in solids, for future synthetic exploitation.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4DT00408F
Abstract: A series of eight 5-(TeAr)-6-(SePh)acenaphthenes (Ar = aryl) were prepared and structurally characterised by X-ray crystallography, solution and solid-state NMR spectroscopy and DFT/B3LYP calculations.
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2DT31971C
Abstract: Reaction chemistry of an extremely sterically encumbered phosphinic chloride (Mes*)(2)P(=O)Cl (Mes* = 2,4,6-tri-t-butylphenyl, supermesityl) was investigated. This compound, as well as other compounds bearing two supermesityl groups placed geminally at the central phosphorus atom, shows extremely low reactivity at the phosphorus centre. Nevertheless, some synthetically significant transformations were possible. Reduction with hydridic reagents under forcing conditions yielded the phosphine oxide (Mes*)(2)P(=O)H and a secondary phosphine Mes*(2,4-tBu(2)C(6)H(3))PH. Deprotonation of (Mes*)(2)P(=O)H gave the corresponding phosphinite, which afforded very crowded tertiary phosphine oxides (Mes*)(2)P(=O)R (R = Me and Et) on reactions with electrophiles. While the reaction of the phosphine Mes*(2,4-tBu(2)C(6)H(3))PH with sulfur was surprisingly facile (although under forcing conditions), we have been unable to chlorinate or deprotonate this phosphine. All new compounds were fully characterised with multinuclear NMR, IR, Raman, MS, microanalyses and single crystal X-ray diffraction. Our computations (B3LYP and M06-2X level) show that strain energies of (synthetically accessible) geminally substituted compounds are extremely high (180 to 250 kJ mol(-1)), the majority of the strain is stored as boat distortions to the phenyl rings in Mes* substituents.
Publisher: American Chemical Society (ACS)
Date: 29-07-2014
DOI: 10.1021/IC501142V
Abstract: Coordination chemistry of an acenaphthene peri-backbone-supported phosphino-phosphonium chloride (1) was investigated, revealing three distinct modes of reactivity. The reaction of 1 with Mo(CO)4(nor) gives the Mo(0) complex [(1)Mo(CO)4Cl] (2), in which the ligand 1 exhibits monodentate coordination through the phosphine donor and the P-P bond is retained. PtCl2(cod) reacts with the chloride and triflate salts of 1 to form a mononuclear complex [(1Cl)PtCl2] (3) and a binuclear complex [((1Cl)PtCl)2][2TfO] (4), respectively. In both of these complexes, the platinum center adds across the P-P bond, and subsequent chloride transfer to the phosphenium center results in phosphine-chlorophosphine bidentate coordination. [((1)PdCl)2] (5) was isolated from the reaction of 1 and Pd2(dba)3 (dba = dibenzylideneacetone). Oxidative addition to palladium(0) results in a heteroleptic phosphine bridging phosphide coordination to the Pd(II) center. In addition, reaction of 1 with BH3·SMe2 leads to the bis(borane) adduct of the corresponding mixed tertiary/secondary phosphine (6), with BH3 acting as both a reducing agent and a Lewis acid. The new compounds were fully characterized, including X-ray diffraction. The ligand properties of 1 and related bonding issues are discussed with help of DFT computations.
Publisher: Wiley
Date: 28-06-2018
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5DT00159E
Abstract: Reactions of the dianions [ t BuN(E)P(μ-N t Bu)] 2 2− (E = Se,S) with M( i ) reagents (M = Ag, Au) or HgCl 2 produce complexes of [ t Bu(H)N(E)P(μ-N t Bu) 2 P(E)N t Bu] − with spirocyclic, macrocyclic or ladder structures.
Publisher: American Chemical Society (ACS)
Date: 20-08-2014
DOI: 10.1021/JO5015678
Abstract: The synthesis of rigid symmetric polyradical model systems with inter-spin distances between 1.4 and 4 nm and their room temperature continuous wave (CW) EPR spectra are reported. Conditions for attachment of the spin-label via esterification have been optimized on the direct synthesis of polyradicals from commercially available polyphenols and the carboxylic acid functionalized nitroxide TPC. A common synthetic protocol utilizing 4-hydroxy-4'-iodobiphenyl as a key building block has been used to synthesize an equilateral biradical and a triradical in only two steps from commercially available starting materials. The first synthesis of a tetraradical based upon an adamantane core bearing six equivalent nitroxide-nitroxide distances is also reported. These systems are very promising candidates for studying multi-spin effects in pulsed EPR distance measurements.
Publisher: Wiley
Date: 22-12-2014
Abstract: Three related series of peri-substituted bis(tellurides) bearing naphthalene, acenaphthene and acenaphthylene backbones (Nap/Acenap/Aceyl(TeY)2 (Nap = naphthalene-1,8-diyl N Acenap = acenaphthene-5,6-diyl A Aceyl = acenaphthylene-5,6-diyl Ay Y = Ph 1 Fp 2 Tol 3 An-p- 4 An-o- 5 Tp 6 Mes 7 Tip 8) have been synthesised and their solid-state structures determined by X-ray crystallography. Molecular conformations were classified as a function of the two C9-C-Te-C(Y) dihedral angles (θ) in the solid all members adopt AB or CCt configurations, with larger Te(aryl) moieties exclusively imposing the CCt variant. Exceptionally large J((125)Te,(125)Te) spin-spin coupling constants between 3289-3848 Hz were obtained for compounds substituted by bulky Te(aryl) groups, implying these species are locked in a CCt-type conformation. In contrast, compounds incorporating smaller Te(aryl) moieties are predicted to be rather dynamic in solution and afford much smaller J values (2050-2676 Hz), characteristic of greater populations of AB conformers with lower couplings. This conformational dependence of through-space coupling is supported by DFT calculations.
Publisher: American Chemical Society (ACS)
Date: 18-04-2014
DOI: 10.1021/JA502625Z
Abstract: A proximate Lewis basic group facilitates the mild dehydrogenative P-As intramolecular coupling in the phosphine-arsine peri-substituted acenaphthene 3, affording thermally and hydrolytically stable arsanylidine-phosphorane 4 with a sterically accessible two-coordinate arsenic atom. The formation of 4 is thermoneutral due to the dehydrogenation being concerted with the donor coordination. Reaction of 4 with a limited amount of oxygen reveals arsinidene-like reactivity via formation of cyclooligoarsines, supporting the formulation of the bonding in 4 as base-stabilized arsinidene R3P→AsR.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3DT52385C
Abstract: There are only limited reports on vanadium(iv) oxyfluorides (VOFs) with extended crystal structures. Here we expand and enrich the list of existing VOFs with a series of 14 new materials "VOF-n (n = 1-14)" prepared using ionothermal and solvothermal synthesis methods. All of these materials arise from the condensation of a dimeric structural motif. These VOFs can be classified into three groups depending on their key structural features layer structures: VOF-1"[HN2C7H6][V2O2F5]", VOF-2"[HN2C4H4][V2O2F5]", VOF-3"[HN2C3H4][V2O2F5]" and VOF-4"V2(N2C4H4)O2F4", ladder like structures: VOF-5"[NH4(HN2C3H4)][V2O2F6]", VOF-6"[K(HN2C3H4)][V2O2F6]", VOF-7"[HNH2CH2CH3][VOF3]", VOF-8"[HN2C7H6][VOF3]", VOF-9"[H2N2C4H6][V2O2F6]", VOF-10"β-RbVOF3", VOF-11"α-KVOF3", VOF-12"β-KVOF3", VOF-13"[H2(NH2)2(CH2)2][V2O2F6]", and a chain structure: VOF-14"[H2N2C6H12][V2O2F7]". The crystal structures of VOF-n are presented, and their synthetic and structural relationships are discussed.
Location: United Kingdom of Great Britain and Northern Ireland
Location: United Kingdom of Great Britain and Northern Ireland
No related grants have been discovered for Kasun Sankalpa Athukorala Arachchige.