|Title||Highly Active Titanocene Catalysts for Epoxide Hydrosilylation: Synthesis, Theory, Kinetics, EPR Spectroscopy|
|Publication Type||Journal Article|
|Year of Publication||2016|
|Authors||D. Henriques SG, Zimmer K., Klare S., Meyer A., Rojo-Wiechel E., Bauer M., Sure R., Grimme S., Schiemann O., Flowers R.A, Gansauer A.|
|Journal||Angewandte Chemie International Edition|
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.