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Nearly Planar Nonsolvated Monomeric Silyl- and Germyllithiums as a Result of an Intramolecular CH−Li Agostic Interaction

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Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
Cite this: J. Am. Chem. Soc. 2002, 124, 51, 15160–15161
Publication Date (Web):November 26, 2002
https://doi.org/10.1021/ja021142r
Copyright © 2002 American Chemical Society
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Abstract

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Pale-yellow crystals of the nonsolvated monomeric silyl- and germyllithiums, tris[di-tert-butyl(methyl)silyl]silyllithium 2a and tris[di-tert-butyl(methyl)silyl]germyllithium 2b, were obtained by one-electron reduction of the corresponding silyl and germyl radicals with lithium in hexane. The crystal structure analysis of both 2a and 2b showed almost planar geometry around the anionic centers, due to both intramolecular CH−Li agostic interactions and steric reasons. However, the free anions [(tBu2MeSi)3Si-][Li+(THF)4] 3a and [(tBu2MeSi)3Ge-][Li+(THF)n] (n = 3, 4) 3b no longer showed a planar geometry, because of the absence of the intramolecular CH−Li agostic interaction. A temperature-dependent 1H NMR study of 2a showed that the CH−Li interaction is weak.

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 To whom correspondence should be addressed. E-mail:  [email protected] staff.chem.tsukuba.ac.jp.

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Experimental procedure and spectral data of 3a and 3b, temperature-dependent 1H NMR chart of 2a and kinetic data, tables of crystallographic data including atomic positional and thermal parameters for 2a, 2b, 3a, and 3b (PDF). A crystallographic file in CIF format is also available. This material is available free of charge via the Internet at http://pubs.acs.org.

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