(18-C-6)K][(N≡C)CuI -SiMe2 Ph], a Potassium Silylcyanocuprate as a Catalyst Model for Silylation Reactions with Silylboranes: Syntheses, Structures, and Catalytic Properties

Inorganic Chemistry
Jacqueline Plotzitzka, Christian Kleeberg

Abstract

CuI-catalyzed silylation reactions involving silylboranes (in particular, pinB-SiMe2Ph (1)) as silyl sources have recently gained considerable attention. One of the most efficient and versatile and yet simplest catalyst systems consists of CuCN/NaOMe; however, nothing is known about the catalytically relevant species. Using an NHC-based model catalyst, copper silyl complexes of the type [(NHC)Cu-SiMe2Ph] have been established to be crucial species in these catalytic processes. The well-defined and spectroscopically and structurally characterized complex [(18-C-6)K][NC-Cu-OtBu] (2), as a model for the catalytic system, CuCN/NaOMe, shows comparable catalytic activity toward established, exemplary substrates (aldehydes, imines, α,β-unsaturated carbonyls) and in extension allows the efficient silylation of ketones. In addition, a number of peculiarities of the catalytic reaction are readily rationalized on the basis of the mechanistic insight already established using [(NHC)Cu-SiMe2Ph] as a model catalyst. Analogously to the NHC model system, the reaction of 2 with the silylborane 1 furnishes the silylcyanocuprate [(18-C-6)K][NC-Cu-SiMe2Ph] (3) as a potential crucial intermediate in these silylation reactions also suggesting mechan...Continue Reading

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