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The Isolable Cation Radical of Disilene: Synthesis, Characterization, and a Reversible One-Electron Redox System

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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. 2008, 130, 19, 6078–6079
Publication Date (Web):April 19, 2008
https://doi.org/10.1021/ja801761w
Copyright © 2008 American Chemical Society
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Abstract

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The highly twisted tetrakis(di-tert-butylmethylsilyl)disilene 1 was treated with Ph3C+·BAr4− (BAr4−: TPFPB = tetrakis(pentafluorophenyl)borate) in toluene, producing disilene cation radical 3 upon one-electron oxidation. Cation radical 3 was isolated in the form of its borate salt as extremely air- and moisture-sensitive red-brown crystals. The molecular structure of 3 was established by X-ray crystallography, which showed a highly twisted structure (twisting angle of 64.9°) along the central Si−Si bond with a bond length of 2.307(2) Å, which is 2.1% elongated relative to that of 1. The cation radical is stabilized by σ−π hyperconjugation by the four tBu2MeSi groups attached to the two central sp2-Si atoms. An electron paramagnetic resonance (EPR) study of the hyperfine coupling constants (hfcc) of the 29Si nuclei indicates delocalization of the spin over the central two Si atoms. A reversible one-electron redox system between disilene, cation radical, and anion radical is also reported.

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Experimental procedures and EPR spectrum of 3, table of crystallographic data including atomic positional and thermal parameters for 3 (PDF/CIF), computational results of 4 and 5, and molecular orbitals (SOMO) of 3 and 5. This material is available free of charge via the Internet at http://pubs.acs.org.

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