Highly Active Titanocene Catalysts for Epoxide Hydrosilylation: Synthesis, Theory, Kinetics, EPR Spectroscopy

TitleHighly Active Titanocene Catalysts for Epoxide Hydrosilylation: Synthesis, Theory, Kinetics, EPR Spectroscopy
Publication TypeJournal Article
Year of Publication2016
AuthorsD. Henriques SG, Zimmer K., Klare S., Meyer A., Rojo-Wiechel E., Bauer M., Sure R., Grimme S., Schiemann O., Flowers R.A, Gansauer A.
JournalAngewandte Chemie International Edition
Abstract

A catalytic system for titanocene-catalyzed epoxide hydrosilylation is described. It features a straightforward preparation of titanocene hydrides that leads to a reaction with low catalyst loading, high yields, and high selectivity of radical reduction. The mechanism was studied by a suite of methods, including kinetic studies, EPR spectroscopy, and computational methods. An unusual resting state leads to the observation of an inverse rate order with respect to the epoxide.

DOI10.1002/anie.201601242