In the past several years, the Thomas group has been studying a Zr/Co heterobimetallic system featuring a unique dative metal-metal interaction with reactivity substantially different from the corresponding monometallic compounds. Notably, catalysts of the form (THF)Zr(ArNPR2)3Co�N2 have been shown to undergo one-electron redox processes and efficiently affect the hydrosilylation of various ketones in high yield. We believe that this proceeds via homolytic cleavage of the Zr-Co bond and one-electron reduction of the ketone to form a Zr-bound ketyl radical intermediate. This proposed mechanism is supported by the isolation of a tetrametallic asymmetric isobenzopinacol product upon reaction with benzophenone. It is highly desirable to us to induce selectivity at the newly formed stereocenter by altering the ligand environment around the radical species. We describe our recent progress towards preforming this transformation asymmetrically.

Progress towards asymmetric hydrosilylation of ketones using a Zr/Co heterobimetallic complex

247th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.