Platinum Catalysis Revisited-Unraveling Principles of Catalytic Olefin Hydrosilylation

Hydrosilylation of C-C multiple bonds is one of the most important applications of homogeneous catalysis in industry. The reaction is characterized by its atom-efficiency, broad substrate scope, and widespread application. To date, industry still relies on highly active platinum-based systems that were developed over half a century ago. Despite the rapid evolution of vast synthetic applications, the development of a fundamental understanding of the catalytic reaction pathway has been difficult and slow, particularly for the industrially highly relevant Karstedt's catalyst. A detailed mechanistic study unraveling several new aspects of platinum-catalyzed hydrosilylation using Karstedt's catalyst as platinum source is presented in this work. A combination of ²H-labeling experiments, ¹⁹⁵Pt NMR studies, and an in-depth kinetic study provides the basis for a further development of the well-established Chalk-Harrod mechanism. It is concluded that the coordination strength of the olefin exerts a decisive effect on the kinetics of the reaction. In addition, it is demonstrated how distinct structural features of the active catalyst species can be derived from kinetic data. A primary kinetic isotope effect as well as a characteristic product distribution in deuterium-labeling experiments lead to the conclusion that the rate-limiting step of platinum-catalyzed hydrosilylation is in fact the insertion of the olefin into the Pt-H bond rather than reductive elimination of the product in the olefin/silane combinations studied.