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Article Dans Une Revue Journal of the American Chemical Society Année : 2020

From a (Silatrigerma)cyclobutenylium Ion to a (Silatrigerma)cyclobutenyl Radical and Back

Résumé

(Silatrigerma)cyclobutenylium ion salt 2+·[B(C6F5)4]– was readily prepared by the reaction of cyclotrigermene 1 with an equimolar amount of [Et3Si(benzene)]+·[B(C6F5)4]− in benzene. The homoaromatic nature of 2+ was firmly established by its crystallographic analysis, which revealed a highly folded SiGe3 four-membered ring (40.4°) and a remarkably short transannular Ge–Ge distance of 2.9346(3) Å. The homoaromaticity of 2+ was supported by DFT calculations, which confirmed an extensive transannular bonding orbital interaction. One-electron reduction of 2+·[B(C6F5)4]– with potassium graphite resulted in the selective formation of (silatrigerma)cyclobutenyl free radical 2·, which has an allylic-type structure as confirmed by its X-ray and EPR studies. Cation 2+ and free radical 2· can be readily interconverted, thus constituting a fully reversible redox pair.
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Dates et versions

hal-03233933 , version 1 (25-05-2021)

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Vladimir Ya. Lee, Yuki Ito, Olga Gapurenko, Ruslan Minyaev, Heinz Gornitzka, et al.. From a (Silatrigerma)cyclobutenylium Ion to a (Silatrigerma)cyclobutenyl Radical and Back. Journal of the American Chemical Society, 2020, 142 (38), pp.16455-16460. ⟨10.1021/jacs.0c08052⟩. ⟨hal-03233933⟩
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