The isolable cation radical of disilene: synthesis, characterization, and a reversible one-electron redox system

Journal of the American Chemical Society
Shigeyoshi InoueAkira Sekiguchi

Abstract

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 degrees) along the central Si-Si bond with a bond length of 2.307(2) A, which is 2.1% elongated relative to that of 1. The cation radical is stabilized by sigma-pi 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.

References

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Citations

Aug 27, 2009·Chemical Communications : Chem Comm·Yuzhong Wang, Gregory H Robinson
Sep 3, 2016·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Tatsumi OchiaiShigeyoshi Inoue
Dec 24, 2016·Inorganic Chemistry·Shu-Hua ZhangCheuk-Wai So
Nov 10, 2015·Chemistry : a European Journal·Soichiro Kyushin, Akihiro Tsurusaki
Nov 21, 2015·Chemical Society Reviews·Kartik Chandra MondalHerbert W Roesky
Apr 6, 2017·Chemistry : a European Journal·Vitaly NesterovShigeyoshi Inoue
Jul 30, 2014·Chemical Communications : Chem Comm·Syed Usman AhmadShigeyoshi Inoue
Jul 2, 2014·Chemistry : a European Journal·Johann HlinaViatcheslav V Jouikov
Jul 4, 2009·Chemistry : a European Journal·Annemarie SchäferJames Y Becker
Jun 10, 2014·Chemistry : a European Journal·Kanako TairaAkira Sekiguchi
Aug 1, 2016·Chemical Science·Marius I ArzAlexander C Filippou
Mar 24, 2018·Nature Communications·Julian BöhnkeHolger Braunschweig
Aug 13, 2009·Physical Chemistry Chemical Physics : PCCP·Joceline Zeitouny, Viatcheslav Jouikov
Jan 10, 2018·Angewandte Chemie·Hui ZhaoDavid Scheschkewitz
Jun 5, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Richard HolznerShigeyoshi Inoue
Jul 3, 2021·Inorganic Chemistry·Mohd NazishHerbert W Roesky
Nov 13, 2010·Journal of the American Chemical Society·Jonathan JeckDavid Scheschkewitz

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