Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

5-23-2012

Journal or Book Title

Journal of the American Chemical Society

Volume

134

Issue

22

First Page

9154

Last Page

9156

DOI

10.1021/ja302226c

Abstract

Salt metathesis reactions of Cp2(NR2)ZrX (X = Cl, I, OTf) and lithium hydrosilazides ultimately afford hydride products Cp2(NR2)ZrH that suggest unusual β-hydrogen elimination processes. A likely intermediate in one of these reactions, Cp2Zr[N(SiHMe2)t-Bu][N(SiHMe2)2], is isolated under controlled synthetic conditions. Addition of alkali metal salts to this zirconium hydrosilazide compound produces the corresponding zirconium hydride. However as conditions are varied, a number of other pathways are also accessible, including C–H/Si–H dehydrocoupling, γ-abstraction of a CH, and β-abstraction of a SiH. Our observations suggest that the conversion of (hydrosilazido)zirconocene to zirconium hydride and silanimine does not follow the classical four-center mechanism for β-elimination.

Comments

Reprinted (adapted) with permission from Journal of the American Chemical Society 134 (2012): 9154, doi: 10.1021/ja302226c. Copyright 2012 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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