From a (Silatrigerma)cyclobutenylium Ion to a (Silatrigerma)cyclobutenyl Radical and Back
- Vladimir Ya. Lee*Vladimir Ya. Lee*[email protected]Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, JapanMore by Vladimir Ya. Lee,
- Yuki ItoYuki ItoDepartment of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, JapanMore by Yuki Ito,
- Olga A. GapurenkoOlga A. GapurenkoInstitute of Physical and Organic Chemistry, Southern Federal University, Rostov on Don 344090, Russian FederationMore by Olga A. Gapurenko,
- Ruslan M. MinyaevRuslan M. MinyaevInstitute of Physical and Organic Chemistry, Southern Federal University, Rostov on Don 344090, Russian FederationMore by Ruslan M. Minyaev,
- Heinz Gornitzka , and
- Akira Sekiguchi*Akira Sekiguchi*[email protected]Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, JapanMore by Akira Sekiguchi
Abstract
(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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This article is cited by 2 publications.
- Bin Li, Christoph Wölper, Gebhard Haberhauer, Stephan Schulz. Synthesis and Reactivity of Heteroleptic Ga‐P‐C Allyl Cation Analogues. Angewandte Chemie 2021, 133 (4) , 2014-2019. https://doi.org/10.1002/ange.202012595
- Bin Li, Christoph Wölper, Gebhard Haberhauer, Stephan Schulz. Synthesis and Reactivity of Heteroleptic Ga‐P‐C Allyl Cation Analogues. Angewandte Chemie International Edition 2021, 60 (4) , 1986-1991. https://doi.org/10.1002/anie.202012595