Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

2-22-2013

Journal or Book Title

Organometallics

Volume

32

Issue

5

First Page

1300

Last Page

1316

DOI

10.1021/om3010299

Abstract

A series of organometallic compounds containing the tris(dimethylsilyl)methyl ligand are described. The potassium carbanions KC(SiHMe2)3 and {KC(SiHMe2)3TMEDA}2 are synthesized by deprotonation of the hydrocarbon HC(SiHMe2)3 with potassium benzyl. {KC(SiHMe2)3TMEDA}2 crystallizes as a dimer with two types of three-center–two-electron K–H–Si interactions: side-on coordination of SiH (∠K–H–Si = 102(2)°) and more obtuse K–H–Si structures (∠K–H–Si ≈ 150°). The divalent calcium and ytterbium compounds M{C(SiHMe2)3}2L (M = Ca, Yb; L = 2THF, TMEDA) are prepared from MI2 and 2 equiv of KC(SiHMe2)3. Low 1JSiH coupling constants in the NMR spectra, low-energy νSiH bands in the IR spectra, and short M–Si distances and small M–C–Si angles in the crystal structures suggest β-agostic interactions on each C(SiHMe2)3 ligand. The IR assignments of M{C(SiHMe2)3}2L (L = 2THF, TMEDA) are supported by DFT calculations. The compounds M{C(SiHMe2)3}2L react with 1 or 2 equiv of B(C6F5)3 to give the 1,3-disilacyclobutane {Me2SiC(SiHMe2)2}2 and MC(SiHMe2)3HB(C6F5)3L or M{HB(C6F5)3}2L, respectively. In addition, M{C(SiHMe2)3}2L compounds react with BPh3 to give β-H abstracted products. The compounds M{C(SiHMe2)3}2THF2 react with SiMe3I to yield Me3SiH and disilacyclobutane as the products of β-H abstraction, while M{C(SiHMe2)3}2TMEDA and Me3SiI form a mixture of Me3SiH and the alkylation product Me3SiC(SiHMe2)3 in a 1:3 ratio.

Comments

Reprinted (adapted) with permission from Organometallics 32 (2013): 1300, doi: 10.1021/om3010299. Copyright 2013 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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