Crystal structures of tris(tert-butyl)boron, -aluminum, -gallium, and -indium:: Nonplanarity of the AlC3 skeleton and evidence of inter- and intramolecular "Agostic" or hyperconjugative interactions

被引:26
作者
Cowley, AR
Downs, AJ
Marchant, S
Macrae, VA
Taylor, RA
机构
[1] Univ Oxford, Inorgan Chem Lab, Oxford OX1 3QR, England
[2] Univ Edinburgh, Sch Chem, Edinburgh EH9 3JJ, Midlothian, Scotland
关键词
D O I
10.1021/om050572y
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
X-ray crystal structures determined at low temperatures (150-220 K) for the tris(tertbutyl) derivatives of boron, aluminum, gallium, and indium (M) reveal essentially monomeric molecular units throughout with consistently longer M-C bonds than in the corresponding monomeric trimethyl derivatives. Comparison of the three structures shows a significant strengthening of intermolecular M(...)beta-CH3 binding in the order M = B similar to Ga < In < Al, resulting in a distinctly nonplanar MC3 skeleton with the M atom displaced 0.25 angstrom above the plane of the quaternary C atoms in the case where M = Al. Tilting of the tert-butyl groups about the M-C bonds, which is concerted when M = B or Al, appears to reflect the influence of intramolecular hyperconjugation or "agostic" bonding.
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页码:5702 / 5709
页数:8
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