REDISTRIBUTION OF METHYL-GROUPS BETWEEN SILICON CENTERS IN BIS(SILYL)TUNGSTEN COMPLEXES - SILYL SILYLENE COMPLEX INTERMEDIATES AS THE SOURCE OF INTERLIGAND REACTIVITY

被引：50

作者：

PESTANA, DC

KOLOSKI, TS

BERRY, DH

机构：

[1] UNIV PENN,DEPT CHEM,PHILADELPHIA,PA 19104

[2] UNIV PENN,RES STRUCT MATTER LAB,PHILADELPHIA,PA 19104

来源：

ORGANOMETALLICS | 1994年 / 13卷 / 11期

关键词：

D O I：

10.1021/om00023a018

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The bis(silyl) complexes Cp(2)W(SiMe(3))(SiR(2)X) (R = i-Pr, CH3, CD3, X = Cl, OSO2CF3) isomerize thermally to bis(silyls) Cp(2)W(SiMe(2)X)(SiR(2)Me), with rates strongly dependent on the nature of R and X, solvent polarity, and the presence of strong Lewis acid catalysts such as B(C6F5)(3). A mechanism is proposed in which an electrophilic cationic silyl(silylene)tungstenocene intermediate is formed by dissociation of X(-), followed by migration of a methyl group to the electrophilic silylene center, and finally reassociation of X(-) to the other silicon to complete the process.

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页码：4173 / 4175

页数：3

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