Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

7-15-2013

Journal or Book Title

Organometallics

Volume

32

Issue

22

First Page

6834

Last Page

6843

DOI

10.1021/om400447q

Abstract

Charge and ancillary ligands affect the reactivity of monomeric tris(trimethylsilyl)silyl magnesium compounds. Diamine-coordinated (tmeda)Mg{Si(SiMe3)3}Me (tmeda = tetramethylethylenediamine; 2-tmeda) and (dpe)Mg{Si(SiMe3)3}Me (dpe =1,2-N,N-dipyrrolidenylethane; 2-dpe) are synthesized by salt elimination reactions of L2MgMeBr and KSi(SiMe3)3. Compounds 2-tmeda or 2-dpe react with MeI or MeOTf to give MeSi(SiMe3)3 as the product of Si–C bond formation. In contrast, 2-tmeda and 2-dpe undergo exclusively reaction at the magnesium methyl group with electrophiles such as Me3SiI, B(C6F5)3, HB(C6F5)2, and [Ph3C][B(C6F5)4]. These reactions provide a series of neutral, zwitterionic, and cationic magnesium silyl compounds, and from this series we have found that silyl group transfer is less effective with cationic magnesium compounds than neutral complexes.

Comments

Reprinted (adapted) with permission from Organometallics 32 (2013): 6834, doi: 10.1021/om400447q. Copyright 2013 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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