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An Isolable NHC-Stabilized Silylene Radical Cation: Synthesis and Structural Characterization

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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. 2012, 134, 12, 5540–5543
Publication Date (Web):March 15, 2012
https://doi.org/10.1021/ja301180v
Copyright © 2012 American Chemical Society
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Abstract

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The silyl-substituted silylene–NHC complex bis(tri-tert-butylsilyl)silylene–(1,3,4,5-tetramethylimidazol-2-ylidene) [(tBu3Si)2Si:←NHCMe, 2] was synthesized and isolated as air- and moisture-sensitive orange crystals by reductive debromination of the dibromosilane (tBu3Si)2SiBr2 (1) with 2.0 equiv of KC8 in the presence of NHCMe. In addition, the silylene–NHC complex 2 cleanly underwent one-electron oxidation with 1.0 equiv of Ph3C+·Ar4B– (Ar4B– = tetrakis[4-(tert-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl]borate) in benzene to afford the NHC-stabilized silylene radical cation [(tBu3Si)2Si←NHCMe]•+·Ar4B– (3). The radical cation 3 was isolated as air- and moisture-sensitive yellow crystals and structurally characterized by X-ray crystallography and electron paramagnetic resonance spectroscopy, which showed that 3 has a planar structure with a π-radical nature.

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The experimental procedures of 2 and 3; UV–vis spectrum of 2; natural population analysis of 2 and 3; tables of crystallographic data, including atomic positional and thermal parameters, and CIFs for 2 and 3. This material is available free of charge via the Internet at http://pubs.acs.org.

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