Fluorosilane Activation by Pd/Ni→Si-F→Lewis Acid Interaction: An Entry to Catalytic Sila-Negishi Coupling

A new mode of bond activation involving M→Z interactions is disclosed. Coordination to transition metals as σ-acceptor ligands was found to enable the activation of fluorosilanes, opening the way to the first transition-metal-catalyzed Si-F bond activation. Using phosphines as directing groups, sila-Negishi couplings were developed by combining Pd and Ni complexes with external Lewis acids such as MgBr₂. Several key catalytic intermediates have been authenticated spectroscopically and crystallographically. Combined with DFT calculations, all data support cooperative activation of the fluorosilane via Pd/Ni→Si-F→Lewis acid interaction with conversion of the Z-type fluorosilane ligand into an X-type silyl moiety.