Reversible Silylium Transfer between P-H and Si-H Donors

Abstract

The Mo=PR₂ π* orbital in a Mo phosphenium complex acts as acceptor in a new P^III -based Lewis superacid. This Lewis acid (LA) participates in electrophilic Si-H abstraction from E₃ SiH to give a Mo-bound secondary phosphine ligand, Mo-PR₂ H. The resulting Et₃ Si⁺ ion remains associated with the Mo complex, stabilized by η¹ -P-H donation, yet undergoes rapid exchange with an η¹ -Si-H adduct of free silane in solution. The equilibrium between these two adducts presents an opportunity to assess the role of this new LA in catalytic reactions of silanes: is the LA acting as a catalyst or as an initiator? Preliminary results suggest that a cycle including the Mo-bound phosphine-silylium adduct dominates in the catalytic hydrosilylation of acetophenone, relative to a putative cycle involving the silane-silylium adduct or "free" silylium.

Keywords: Lewis acids; Si-H activation; hydrosilylation; phosphenium complex; silylium adduct.