Mechanistic details on a hydrosilylation reaction between 1-butene and Et<sub>2</sub>SiH<sub>2</sub> catalyzed by a cationic nickel allyl complex (Fig. 1) have been investigated with density functional theory (DFT). Results of the DFT calculation show that the hydrosilylation begins with dissociation of the arene ligand followed by cleavage of a Si-H bond. The results suggest that the Si-H cleavage step should be described as hydride transfer from the Si-H moiety to the nickel center where the process occurs without forming a Ni-Si bond. Natural bond orbital population analysis indicates that both Ni and Si atoms in the complex are cationic in nature, thereby inducing the electrostatic repulsion between them during the catalytic process. Thus, oxidative addition of the silane to the metal is prohibited in the present catalyst. After the Si-H cleavage, the silicon atom is coordinated by the neighboring allyl ligand as described in Scheme 1. As far as we know, such a ligand participation during a hydrosilylation reaction is not found in any of known hydrosilylation mechanisms, indicating the novelty of the present mechanism.

Analysis on olefin hydrosilylation catalyzed by a cationic nickel allyl complex

251st National Meeting (2016)

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