Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

8-2015

Journal or Book Title

Dalton Transactions

Volume

44

Issue

36

First Page

15897

Last Page

15904

DOI

10.1039/c5dt02844b

Abstract

An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ3-N,Si,C-PhB(OxMe2)(OxMe2SiHPh)ImMes}Rh(H)CO][HB(C6F5)3] (2, OxMe2 = 4,4-dimethyl-2-oxazoline; ImMes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(OxMe2)2ImMes}RhH(SiH2Ph)CO (1) and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(OxMe2)2ImMes}RhH(SiHPh)CO][HB(C6F5)3] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C6F5)3 catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH3 as the reducing agent.

Comments

This article is from Dalton Transactions 44 (2015): 15897, doi:10.1039/c5dt02844b. Posted with permission.

Rights

This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Copyright Owner

Royal Society of Chemistry

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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