Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

5-20-2011

Journal or Book Title

ACS Catalysis

Volume

1

Issue

7

First Page

698

Last Page

702

DOI

10.1021/cs2001016

Abstract

The four-coordinate zinc compound ToMZnH (1, ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate) catalyzes selective alcoholysis of substituted hydrosilanes. The catalytic reaction of PhMeSiH2 and aliphatic alcohols favors the monodehydrocoupled product PhMeHSi–OR. With the aryl alcohol 3,5-C6H3Me2OH, the selectivity for mono(aryloxy)hydrosilane PhMeHSiOC6H3Me2 and bis(aryloxy)silane PhMeSi(OC6H3Me2)2 is controlled by relative reagent concentrations. Reactions of secondary organosilanes and diols provide cyclic bis(oxo)silacycloalkanes in high yield. The empirical rate law for the ToMZnH-catalyzed reaction of 3,5-dimethylphenol and PhMeSiH2 is −d[PhMeSiH2]/dt = k′obs[ToMZnH]1[3,5-C6H3Me2OH]0[PhMeSiH2]1 (determined at 96 °C) which indicates that Si–O bond formation is turnover-limiting in the presence of excess phenol.

Comments

Reprinted (adapted) with permission from ACS Catalysis 1 (2011): 698, doi: 10.1021/cs2001016. Copyright 2011 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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