Gallium(III)/Antimony(III) C-Centered Geminal Organodimetallic Complexes

Philip C. Andrews, Peter J. Nichols

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Abstract

The 1,2-addition of Me3Ga in thf to the stiba-alkene species [2-Pyr(SiMe3)2CSb=C(SiMe3)2-Pyr] results in the mixed Sb/Ga geminal C-centered organodimetallic complex {[2-Pyr(SiMe3)2]-CSb(Me)C[2-Pyr(SiMe 3)]Ga(Me)2} (Pyr = C5H4N), 2, which on heating eliminates CH4 to form a new Sb/Ga geminal organodimetallic complex adopting a structure with a distorted bicyclo[2.2.2]-type core, 3. Both complexes have been structurally authenticated by single-crystal X-ray diffraction; 2 is isostructural with its Al analogue in forming a bimetallic six-membered heterocycle, while CH4 elimination between the -GaMe2 and Me3Si- groups in 2 results in the heterocycle being bridged by a -Ga-CH2-Si- unit and the formation of the new complex, 3. Both complexes are chiral, with 2 being present as both diastereoisomers, R,S and S,R (space group P21/n), while 3 is found exclusively in the R,R configuration, space group P212121. 1H and 13C NMR spectra confirmed the composition of the complexes and revealed that 2 could not be quantitatively converted into 3 without significant decomposition. They also reveal that the structure of 3 is rigid in solution.

Original languageEnglish
Pages (from-to)1277-1281
Number of pages5
JournalOrganometallics
Volume19
Issue number7
Publication statusPublished - 3 Apr 2000

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