π-Bonding and the Lone Pair Effect in Multiple Bonds Involving Heavier Main Group Elements: Developments in the New Millennium

被引：900

作者：

Fischer, Roland C. ^{[1
]}

Power, Philip P. ^{[2
]}

机构：

[1] Graz Univ Technol, A-8010 Graz, Austria

[2] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA

来源：

CHEMICAL REVIEWS | 2010年 / 110卷 / 07期

基金：

美国国家科学基金会;

关键词：

COORDINATED PHOSPHORUS-COMPOUNDS; X-RAY-STRUCTURE; UNSATURATED SILICON-COMPOUNDS; METAL-SUBSTITUTED DIPHOSPHENES; PHOSPHAVINYL GRIGNARD-REAGENTS; CARBON DOUBLE-BOND; ELECTRON-DENSITY DISTRIBUTION; HETEROCYCLIC CARBENE ANALOG; DONOR-STABILIZED SILENES; GALLIUM-GALLIUM BONDS;

D O I：

10.1021/cr100133q

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A review of the study titled 'π-bonding and the lone pair effect in multiple bonds between heavier main group elements', focusing on the synthesis, structure, and bonding of stable compounds of heavier main group elements, is presented. It is found that the red aluminum derivative is generated in solution by a reduction process and this highly reactive molecule undergoes rapid cyclization in toluene. The parent metal amides and related derivatives are prepared by photolysis of Al, Ga, or In atoms and isolated in NH 3-doped frozen argon matrixes. The first experimental evidence for a transiently formed silicon-carbon double bond was depicted through pyrolysis of 1,1-dimethyl-1-silacyclobutane, forming 1,1-dimethylsilene as a transient intermediate. The trisila-allene is characterized by short Si-Si distances of 2.179(3) and 2.206(3) Å, in contrast to the lighter homologues which display a strictly linear arrangement of a bent trisila array.

引用

页码：3877 / 3923

页数：47

共 803 条

[1] Synthesis, structure, and bonding of stable dialkylsilaketenimines [J].