ORCID Profile
0000-0003-0309-0075
Current Organisations
Monash University
,
Wehrwissenschaftliches Institut für Werk- und Betriebsstoffe Erding
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Publisher: CSIRO Publishing
Date: 2020
DOI: 10.1071/CH20129
Abstract: A safer route than that previously published for the synthesis of [BeI2(OEt2)2] has been developed. Reactions of beryllium dihalide complexes [BeX2(OEt2)2] (X=Br or I) with either LiMe or LiBun lead to mixtures of products, which have been shown to act as sources of ‘BeR2’ (R=Me or Bun) in previous synthetic studies. Here, a titration method has been developed to determine the quantity of metal alkyl residues in these ‘BeR2’ mixtures that are available for subsequent alkane elimination reactions. Treating ‘BeMe2’ mixtures with N,N,N′,N′-tetramethylethylenediamine (tmeda) gave two lithium tetramethylberyllate compounds, [{(tmeda)Li}2(μ-BeMe4)] and [{[(tmeda)Li](BeMe4)(μ-Li)}∞], which were crystallographically characterised. Treatment of insitu-generated ‘BeR2’ solutions with several β-diketimines (HC{C(Me)=NR}{=C(Me)N(H)R}, NacnacH, R=aryl or alkyl) yielded a series of β-diketiminato beryllium alkyl complexes, [(Nacnac)BeR], including the first chiral ex le of such a compound. Crystallographic studies of these reveal them to be monomeric, with planar three-coordinate beryllium centres.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1DT02273C
Abstract: Dititanoxycarbene [(TiX 3 ) 2 (μ-CO 2 )] (X = N[ t Bu](3,5-Me 2 C 6 H 3 )) and B(C 6 F 5 ) 3 cleaved dihydrogen under ambient conditions to give the zwitterionic formate [(TiX 3 ) 2 (μ-OCHO-κ O :κ O ′)(B(C 6 F 5 ) 3 )] and the hydrido borate [Ti(N[ t Bu]Ar) 3 ][HB(C 6 F 5 ) 3 ].
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8DT03056A
Abstract: Deprotonation of a formato ligand by cis -coordinated carbyne resulted in the formation of a dioxo complex, CO, ethylene and propylene.
Publisher: Elsevier BV
Date: 03-2017
Publisher: Wiley
Date: 05-11-2020
Abstract: Reactions of two magnesium(I) compounds, [{( Ar Nacnac)Mg} 2 ] ( Ar Nacnac=[HC(MeCNAr) 2 ] − Ar=mesityl (Mes) or o ‐xylyl (Xyl)), with CO in the presence of [Mo(CO) 6 ] lead to the reductive hexamerization of CO, and formation of magnesium benzenehexolate complexes, [{( Ar Nacnac)Mg} 6 (C 6 O 6 )]. [Mo(CO) 6 ] is not consumed in these reactions, but is apparently required to initiate (or catalyze) the CO hexamerizations. A range of studies were used to probe the mechanism of formation of the benzenehexolate complexes. The magnesium(I) reductive hexamerizations of CO are closely related to Liebig's reduction of CO with molten potassium (to give K 6 C 6 O 6 , amongst other products), originally reported in 1834. As the mechanism of that reaction is still unknown, it seems reasonable that magnesium(I) reductions of CO could prove useful homogeneous models for its elucidation, and for the study of other C−C bond forming reactions that use CO as a C 1 feedstock (e.g. the Fischer–Tropsch process).
Publisher: Wiley
Date: 25-06-2015
Abstract: We describe the stable and isolable dimetalloxycarbene [(TiX3 )2 (μ2 -CO2 -κ(2) C,O:κO')] 5, where X=N-(tert-butyl)-3,5-dimethylanilide, which is stabilized by fluctuating μ2 -κ(2) C,O:κ(1) O' coordination of the carbene carbon to both titanium centers of the dinuclear complex 5, as shown by variable-temperature NMR studies. Quantum chemical calculations on the unmodified molecule indicated a higher energy of only +10.5 kJ mol(-1) for the μ2 -κ(1) O:κ(1) O' bonding mode of the free dimetalloxycarbene compared to the μ2 -κ(2) C,O:κ(1) O' bonding mode of the masked dimetalloxycarbene. The parent cationic bridging formate complex [(TiX3 )2 (μ2 -OCHO-κO:κO')][B(C6 F5)4], 4[B(C6 F5)4], was simply deprotonated with the strong base K(N(SiMe3 )2 ) to give 5. Complex 5 reacts smoothly with CO2 to generate the bridging oxalate complex [(TiX3 )2 (μ2 -C2 O4 -κO:κO'')], 6, in a C-C bond formation reaction commonly anticipated for oxalate formation by reductive coupling of CO2 on low-valent transition-metal complexes.
Publisher: Wiley
Date: 02-07-2020
Publisher: Elsevier BV
Date: 08-2018
Publisher: Wiley
Date: 23-10-2018
Abstract: This work focuses on nucleophilic activation of CO
Publisher: American Chemical Society (ACS)
Date: 25-02-2020
Publisher: Wiley
Date: 25-06-2015
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1DT01393A
Abstract: A variety of C- and P-donor adduct complexes of beryllium dihalides have been synthesised. Attempts to reduce these have led to N-heterocyclic carbene adducts of beryllium hydride and naphthalenediyl fragments, and a rare ex le of a Be–Al bonded complex.
Publisher: Wiley
Date: 05-11-2020
Abstract: Reactions of two magnesium(I) compounds, [{( Ar Nacnac)Mg} 2 ] ( Ar Nacnac=[HC(MeCNAr) 2 ] − Ar=mesityl (Mes) or o ‐xylyl (Xyl)), with CO in the presence of [Mo(CO) 6 ] lead to the reductive hexamerization of CO, and formation of magnesium benzenehexolate complexes, [{( Ar Nacnac)Mg} 6 (C 6 O 6 )]. [Mo(CO) 6 ] is not consumed in these reactions, but is apparently required to initiate (or catalyze) the CO hexamerizations. A range of studies were used to probe the mechanism of formation of the benzenehexolate complexes. The magnesium(I) reductive hexamerizations of CO are closely related to Liebig's reduction of CO with molten potassium (to give K 6 C 6 O 6 , amongst other products), originally reported in 1834. As the mechanism of that reaction is still unknown, it seems reasonable that magnesium(I) reductions of CO could prove useful homogeneous models for its elucidation, and for the study of other C−C bond forming reactions that use CO as a C 1 feedstock (e.g. the Fischer–Tropsch process).
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7DT04859A
Abstract: A series of tetravalent titanium complexes supported by the trianionic triamido-amine ligand (Me 3 SiNCH 2 CH 2 ) 3 N 3− including terminal and bridging formate has been prepared and structurally characterized.
Publisher: Wiley
Date: 16-01-2019
Abstract: Reactions of the beryllium dihalide complexes [BeX
Publisher: American Chemical Society (ACS)
Date: 06-12-2018
Publisher: Wiley
Date: 10-07-2019
Abstract: Additions of beryllium-halide bonds in the simple beryllium dihalide adducts, [BeX
Publisher: Wiley
Date: 18-10-2021
Abstract: Reductions of the in situ generated CO and N 2 complexes of Cummins’ molybdenum(III) tris(anilide) complex, viz . [Mo(L){N(Ar’)Bu t } 3 ] (L=CO or N 2 , Ar’=3,5‐dimethylphenyl), using a dimagnesium(I) compound, [{( Mes Nacnac)Mg} 2 ] ( Mes Nacnac=[HC(MeCNMes) 2 ] − , Mes=mesityl), are reported. Reduction of [Mo(CO){N(Ar’)Bu t } 3 ] afforded a mixture of products, three of which were isolated in low yield and crystallographically characterized. These were a molybdenum(II) tris(carbamoyl) complex, [( Mes Nacnac)Mg{μ‐(O=)[Bu t (Ar’)N]C} 3 Mo(CO) 3 ] 1 , a magnesium(II) carbamate, [{( Mes Nacnac)Mg[μ‐O 2 CN(Ar’)Bu t ]} 2 ] 2 , and the 1,3‐diamino‐1,2,3‐trione, Bu t (Ar’)NC 3 (=O) 3 N(Ar’)Bu t 3 . The mechanisms of formation of these products are speculated upon. The reduction of [Mo(N 2 ){N(Ar’)Bu t } 3 ] with [{( Mes Nacnac)Mg} 2 ], in the presence of the N‐heterocyclic carbene, :C{N(Me)C(Me)} 2 TMC, gave the heterobimetallic molybdenum(II) diazenido complex, [( Mes Nacnac)(TMC)Mg(μ‐N 2 )Mo{N(Ar’)Bu t } 3 ] 4 , in a low‐moderate isolated yield. Reaction of this with chlorotrimethylsilane afforded an essentially quantitative yield of the known silyldiazenido complex, [(Me 3 SiN 2 )Mo{N(Ar’)Bu t } 3 ] 5 .
Publisher: American Chemical Society (ACS)
Date: 16-05-2019
DOI: 10.1021/JACS.9B04085
Abstract: This study details syntheses of unsymmetrical magnesium(I)-adduct complexes, [(
Publisher: Wiley
Date: 10-07-2019
Location: Germany
No related grants have been discovered for Albert Paparo.