Article ID Journal Published Year Pages File Type
1322825 Journal of Organometallic Chemistry 2013 9 Pages PDF
Abstract

(NHC)copper(I) hydrides catalyse the hydrosilylation of ketones. (NHC)copper(I) (bi)fluoro species were shown to be active catalysts that do not require an activating agent. In this contribution, the self-activating mechanism of a (NHC)copper(I) (bi)fluoro pre-catalyst has been elucidated by a combined theoretical and experimental study. Experimental NMR studies show the fluorosilane by-product to intervene in the activation mechanism. Thus, bifluoride copper(I) complexes are auto-activating catalysts. Several hypotheses on the activation mechanism have been investigated, and experimental and theoretical results, point towards the formation of a tight ion pair between a difluorosilicate and a cationic copper(I) complex. Results furthermore yield insight into the mechanism of the Cu(I) hydride formation.

Graphical abstractNHC–copper(I) (bi)fluoro species are shown to be auto-active catalysts, with the fluorosilane by-product shown to intervene in the activation mechanism. This self-activating mechanism of (NHC)copper(I) (bi)fluoro pre-catalysts has been elucidated by a combined theoretical and experimental study.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Study on activation step of NHC–copper(I) bifluorides. ► Experimental and theoretical 1H and 19F NMR studies. ► NHC–Cu(I) bifluorides show auto-activating catalytic behaviour. ► Cationic copper(I) complex and difluorosilicate form tight ionic pair.

Related Topics
Physical Sciences and Engineering Chemistry Inorganic Chemistry
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