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Isolable p- and m-[(tBu2MeSi)2Si]2C6H4: Disilaquinodimethane vs Triplet Bis(silyl radical)

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Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
[email protected]
Cite this: J. Am. Chem. Soc. 2011, 133, 15, 5773–5775
Publication Date (Web):March 28, 2011
https://doi.org/10.1021/ja2014746
Copyright © 2011 American Chemical Society
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Abstract

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Isomeric p- and m-disilaquinodimethanes 2 and 4 were synthesized by the reductive dehalogenation of the corresponding p- and m-bis(halosilyl)benzenes 1 and 3, respectively, and were isolated and structurally characterized. The X-ray diffraction and solid-state NMR studies of 2 revealed its singlet quinodimethane structure featuring two exocyclic Si═C double bonds with some singlet biradical contribution. In contrast, the X-ray crystallography and EPR measurements of 4 disclosed its biradical nature, described as a triplet ground state bis(silyl radical).

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Experimental procedures and spectral data for compounds 1−7; tables of crystallographic data, including atomic positional and thermal parameters, and CIF files for 2 and 4; UV−vis spectral charts of 2 and 4; temperature-dependent EPR spectral chart of 4. This material is available free of charge via the Internet at http://pubs.acs.org.

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