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Electron-Induced Conversion of Silylones to Six-Membered Cyclic Silylenes

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posted on 03.12.2014, 00:00 authored by Sudipta Roy, Kartik Chandra Mondal, Lennard Krause, Peter Stollberg, Regine Herbst-Irmer, Dietmar Stalke, Jann Meyer, A. Claudia Stückl, Bholanath Maity, Debasis Koley, Suresh Kumar Vasa, Sheng Qi Xiang, Rasmus Linser, Herbert W. Roesky
A silicon atom in the zero oxidation state stabilized by two carbene ligands is known as sila­dicarbene (silyl­one). There are two pairs of electrons on the silicon atom in silyl­one. This was recently confirmed by both experimental and theoretical charge density investigations. The silyl­one is stable up to 195 °C in an inert atmosphere. However, a substoichiometric amount (33 mol%) of potassium metal triggers the activation of the unsaturated C:Si:C backbone, leading to a selective reaction with a tertiary C–H bond in an atom-economical approach to form a six-membered cyclic silylene with three-coordinate silicon atom. Cyclic voltammetry shows that this reaction proceeds via the formation of a silyl­one radical anion intermediate, which is further confirmed by EPR spectroscopy.