[(18-C-6)K][(N≡C)CuI-SiMe2Ph], a Potassium Silylcyanocuprate as a Catalyst Model for Silylation Reactions with Silylboranes: Syntheses, Structures, and Catalytic Properties.

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 mechanistic similarities between (NHC)Cu- and CuCN/NaOMe-based catalyst systems. Moreover, 3 and [(NHC)Cu-SiMe2Ph] complexes also share structurally distinctive features. In the solid state 3 either exists as a linear, two-coordinated copper complex or, depending on the conditions of crystallization, forms binuclear μ-silyl bridged dimers exhibiting very short Cu···Cu distances. Both structural motifs are also known for [(NHC)Cu-SiR3] complexes. These findings give an initial insight into the versatile structural chemistry of certain silylcyanocuprates; in particular, the finding of dinuclear silylcuprates gives rise to the question whether these dimeric species are of mechanistic relevance for the catalytic processes. However, all peculiarities of the investigated catalytic reaction can readily be rationalized on the basis of the mechanistic details established using (NHC)Cu model complexes.