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Isolable Silylene Anion Radical:  Structural Characteristics in the Solid State and in Solution

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Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
Cite this: J. Am. Chem. Soc. 2007, 129, 19, 6096–6097
Publication Date (Web):April 19, 2007
https://doi.org/10.1021/ja0711314
Copyright © 2007 American Chemical Society
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Abstract

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Tetrakis(di-tert-butylmethylsilyl)disilene (1) was treated with 2.2 equiv of metal naphthalenide (M = Li, Na) in THF. When a crown ether was added to the reaction mixture, the silylene anion radical ((tBuMe2Si)2Si:•- M(crown ether)2+) (2a:  M = Li, 2b:  M = Na) was formed. They were isolated in the form of the lithium or sodium salts as extremely air- and moisture-sensitive red crystals. The structures of 2 were unambiguously characterized by ESR spectroscopic data as well as by X-ray crystallographic analysis. The X-ray crystal structure of 2a reveals free silylene anion radical, showing no interaction with counterion (solvent-separated ion pair). The structures of 2 in solution were also deduced by ESR spectroscopy. The ESR spectra of 2a and 2b in a polar solvent (THF or DME) show a solvent-separated ion pair, whereas the ESR spectrum of 2b in toluene shows contact ion pair owing to the interaction of the counterion with the anionic silicon atom.

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The experimental procedures of 2a and 2b, table of crystallographic data including atomic positional and thermal parameters for 2a (PDF/CIF), optimized geometries of bis(di-tert-butylmethyl)silylene and its anion radical 2. This material is available free of charge via the Internet at http://pubs.acs.org.

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