Hydrosilylation of Olefins Catalyzed by Well-Defined Cationic Aluminum Complexes: Lewis Acid versus Insertion Mechanisms

The cationic aluminum complex [NacNacAlH]+ (2; NacNac = CH­{C­(Me)­N­(2,6-Pri 2C6H3)}2) can be easily generated from NacNacAlH2 by hydride abstraction and functions as a catalyst for the hydrosilylation of olefins and alkynes. Mechanistic studies suggest that, although olefin insertion into the Al–H...

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Bibliographic Details
Published in:ACS catalysis 2016-11, Vol.6 (11), p.7350-7356
Main Authors: Jakobsson, Kayla, Chu, Terry, Nikonov, Georgii I
Format: Article
Language:English
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Summary:The cationic aluminum complex [NacNacAlH]+ (2; NacNac = CH­{C­(Me)­N­(2,6-Pri 2C6H3)}2) can be easily generated from NacNacAlH2 by hydride abstraction and functions as a catalyst for the hydrosilylation of olefins and alkynes. Mechanistic studies suggest that, although olefin insertion into the Al–H bond is very facile, the catalysis does not proceed by an insertion/metathesis mechanism but likely by Lewis acid activation. Stoichiometric reactions of 2 with alkynes furnished unexpected products of CC addition across the NacNacAl moiety to give tripodal aluminum cations, which are also potent catalysts for the hydrosilylation of alkynes.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.6b01694