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

Philip C. Andrews, Peter J. Nichols

Research output: Contribution to journalArticleResearchpeer-review

15 Citations (Scopus)

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

Cite this

@article{63b559fa076941fab456e69604e2a262,
title = "Gallium(III)/Antimony(III) C-Centered Geminal Organodimetallic Complexes",
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.",
author = "Andrews, {Philip C.} and Nichols, {Peter J.}",
year = "2000",
month = "4",
day = "3",
language = "English",
volume = "19",
pages = "1277--1281",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "7",

}

Gallium(III)/Antimony(III) C-Centered Geminal Organodimetallic Complexes. / Andrews, Philip C.; Nichols, Peter J.

In: Organometallics, Vol. 19, No. 7, 03.04.2000, p. 1277-1281.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Gallium(III)/Antimony(III) C-Centered Geminal Organodimetallic Complexes

AU - Andrews, Philip C.

AU - Nichols, Peter J.

PY - 2000/4/3

Y1 - 2000/4/3

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0001045064&partnerID=8YFLogxK

M3 - Article

VL - 19

SP - 1277

EP - 1281

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 7

ER -