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Org Biomol Chem ; 19(25): 5544-5550, 2021 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-34060566

RESUMO

Hydrosilylation of C[double bond, length as m-dash]C double and C[triple bond, length as m-dash]C triple bonds is one of the most widely used processes in organosilicon chemistry, mostly catalyzed by Pt-based complexes. We report here the synthesis of an air-stable dicationic Zn2+-based complex in a hemilabile tris(2-methyl-6-pyridylmethyl) phosphine (TmPPh) ligand, 12+[B(C6F5)4]2. When heated, 12+[B(C6F5)4]2 activates Si-H bonds reversibly via ligand/metal cooperation between Lewis acidic Zn2+ and Lewis basic N centers in a frustrated Lewis pair (FLP) type fashion. Consequently, 12+[B(C6F5)4]2 was found to be an effective catalyst for hydrosilylation reactions of C[double bond, length as m-dash]C double and C[triple bond, length as m-dash]C triple bonds. Remarkably, these hydrosilylation reactions can be loaded under aerobic conditions, as well as, in some cases, work under neat conditions. The mechanism of the activation of the Si-H bond and the hydrosilylation reaction is proposed based on experiments and density functional theory (DFT) calculations.

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