Radical cations of phenyl silatrane

Electrochemical oxidation of phenylsilatrane ( 1 ) in CH 3 CN/0.1 M Bu 4 NPF 6 has been studied by voltammetry, UV-Vis and EPR-coupled spectroelectrochemistry supported by DFT calculations. One-electron withdrawal from the HOMO of 1 , formed with a predominant contribution of the atrane N atom to th...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2017-07, Vol.46 (27), p.8849-8854
Main Authors: Romanovs, Vitalijs, Sidorkin, Valery, Belogolova, Elena, Jouikov, Viatcheslav
Format: Article
Language:English
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Chemical Sciences
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Summary:Electrochemical oxidation of phenylsilatrane ( 1 ) in CH 3 CN/0.1 M Bu 4 NPF 6 has been studied by voltammetry, UV-Vis and EPR-coupled spectroelectrochemistry supported by DFT calculations. One-electron withdrawal from the HOMO of 1 , formed with a predominant contribution of the atrane N atom to the 3c-4e system, results in a short lived radical cation, in which the atrane nitrogen atom is almost planar and carries most of the spin density showing strong coupling with the protons of the axially directed C-H bonds of the three adjacent α-methylene groups ( g = 2.0037, a α H ax = 37.93 G, a α H lat = 0.23 G and a β H = 1.8 G). EPR spectroscopy and DFT calculations attest that the unpaired electron in the radical cation does not reside at the Si atom. Electrochemical oxidation of phenyl silatrane provides persistent radical cations with an unpaired electron mostly localized on the atrane nitrogen.
ISSN:1477-9226
1477-9234
DOI:10.1039/c7dt00447h