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Inorganics 2018, 6(2), 54;

S–H Bond Activation in Hydrogen Sulfide by NHC-Stabilized Silyliumylidene Ions

WACKER-Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching bei München, Germany
Institut für Anorganische Chemie, Goethe-Universität, Max-von-Laue-Straße 7, 60438 Frankfurt/Main, Germany
Author to whom correspondence should be addressed.
Received: 24 April 2018 / Revised: 14 May 2018 / Accepted: 17 May 2018 / Published: 24 May 2018
(This article belongs to the Special Issue Coordination Chemistry of Silicon)
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Reactivity studies of silyliumylidenes remain scarce with only a handful of publications to date. Herein we report the activation of S–H bonds in hydrogen sulfide by mTer-silyliumylidene ion A (mTer = 2,6-Mes2-C6H3, Mes = 2,4,6-Me3-C6H2) to yield an NHC-stabilized thiosilaaldehyde B. The results of NBO and QTAIM analyses suggest a zwitterionic formulation of the product B as the most appropriate. Detailed mechanistic investigations are performed at the M06-L/6-311+G(d,p)(SMD: acetonitrile/benzene)//M06-L/6-311+G(d,p) level of density functional theory. Several pathways for the formation of thiosilaaldehyde B are examined. The energetically preferred route commences with a stepwise addition of H2S to the nucleophilic silicon center. Subsequent NHC dissociation and proton abstraction yields the thiosilaaldehyde in a strongly exergonic reaction. Intermediacy of a chlorosilylene or a thiosilylene is kinetically precluded. With an overall activation barrier of 15 kcal/mol, the resulting mechanistic picture is fully in line with the experimental observation of an instantaneous reaction at sub-zero temperatures. View Full-Text
Keywords: silicon; N-heterocyclic carbenes; silyliumylidenes; small molecule activation; mechanistic insights silicon; N-heterocyclic carbenes; silyliumylidenes; small molecule activation; mechanistic insights

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Porzelt, A.; Schweizer, J.I.; Baierl, R.; Altmann, P.J.; Holthausen, M.C.; Inoue, S. S–H Bond Activation in Hydrogen Sulfide by NHC-Stabilized Silyliumylidene Ions. Inorganics 2018, 6, 54.

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