Highly efficient palladium-catalysed carbon dioxide hydrosilylation employing PMP ligands.

A series of zero-valent palladium complexes featuring diphosphinometal ligands is reported. The metalloligand in the PMP-type framework (M = LiI, CuI, ZnII) acts as a weak to medium acceptor ligand for palladium. A Pd0→ZnII bond was observed in the solid state and further confirmed by NBO analysis. The heterobimetallic Pd/Zn complex 2-Zn displayed excellent activity in chemoselective CO2 hydrosilylation producing silyl formate (TOF1/2 = 3000 h-1).