Synthesis, structure and properties of the Cp2Zr{CH(SiMe3)2}+ cation

被引：6

作者：

Stoebenau, Edward J., III ^{[1
]}

Jordan, Richard F. ^{[1
]}

机构：

[1] Univ Chicago, Dept Chem, Chicago, IL 60637 USA

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2006年 / 691卷 / 23期

基金：

美国国家科学基金会;

关键词：

zirconium; bis(trimethylsilyl)methyl; carborane; dynamic NMR; crystal structure;

D O I：

10.1016/j.jorganchem.2006.08.033

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The generation and properties of the Cp2Zr{CH(SiMe3)(2)}(+) cation are described. An X-ray crystallographic analysis shows that the carborane salt [Cp2Zr{CH(SiMe3)(2)}][HCB11Me5Br6] contains an agostic Zr-mu-Me-Si interaction in the solid state. Low temperature NMR spectra of the borate salt [Cp2Zr{CH(SiMe3)(2)}][B(C6F5)(4)] show that this interaction is retained in solution. Variable temperature NMR spectra establish that the SiMe2(mu-Me) and unbound SiMe3 units of Cp2Zr{CH(SiMe3)(2)}(+) exchange by a "pivot" process involving partial rotation around the Zr-CH(SiMe3)(2) bond, with a barrier of Delta G(double dagger) = 9.2(1) kcal/mol at -89 degrees C. Cp2Zr{CH(SiMe3)(2)}(+) does not coordinate alkenes or alkynes. (c) 2006 Elsevier B.V. All rights reserved.

引用

页码：4956 / 4962

页数：7

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