Mechanism of olefin hydrosilylation catalyzed by [RuCl(NCCH3)5]: A DFT study |
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Authors: | Tell Tuttle Dongqi Wang Jutta Köhler Johann Weis |
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Institution: | a Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim an der Ruhr, Germany b Consortium für Elektrochemische Industrie GmbH, Zielstattstrasse 20, D-81379 München, Germany |
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Abstract: | The hydrosilylation reaction between methyldimethoxysilane and methylvinyldimethoxysilane, catalyzed by the cationic species chloropenta(acetonitrile)ruthenium(II)+ (C1), was investigated with density functional theory (DFT). The Chalk-Harrod, Glaser-Tilley and σ-bond metathesis mechanisms were considered as mechanistic possibilities for the reaction and enthalpy profiles of each pathway were computed for the active form of C1. In contrast to the commonly accepted Chalk-Harrod mechanism of hydrosilylation, the computational results indicate that a σ-bond metathesis mechanism, involving the formation of a hydride analogue of C1, is most favored. The B3LYP calculated activation enthalpy for this pathway (ΔHact = 13.1 kcal/mol) is consistent with the experimental observation that C1 is a reasonable catalyst for this reaction under the applied experimental conditions. |
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Keywords: | Density functional theory B3LYP Ruthenium Hydrosilylation Chalk-Harrod mechanism Glaser-Tilley mechanism σ-Bond metathesis |
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