Ligand-induced decarbonylation in diphosphine-ligated palladium acetates [CHCOPd((PR)CH)] (R = Me and Ph)

A new decarbonylation reaction is observed for [( K 2 -acetate)Pd( K 2 -diphosphine)] + complexes. Gas-phase IR experiments identify the product as [CH 3 Pd(OP(Ph 2 )CH 2 PPh 2 )] + . DFT calculations uncovered a plausible mechanism involving O atom abstraction by the diphosphine ligand within the coordination sphere to yield the acetyl complex, [CH 3 COPd(OP(Ph 2 )CH 2 PPh 2 )] + , which then undergoes decarbonylation. Isotope labelling, IR spectroscopy and DFT calculations reveal a novel ligand-induced decarbonylation reaction.