Selective Alkene Insertion into Inert Hydrogen–Metal Bonds Catalyzed by Mono(phosphorus ligand)palladium(0) Complexes

Isolated mono­(phosphorus ligand)­palladium(0) complexes catalyzed alkene insertions into hydrogen–tungsten bonds. These insertions using WHCp­(CO)₃ with ethyl acrylate and dimethyl fumarate smoothly gave the corresponding alkyltungsten complexes. Kinetic studies involving the stoichiometric reactions and DFT calculations suggest the following steps: (i) formation of a mono­(phosphorus ligand)­mono­(alkene)­palladium(0) species, (ii) subsequent reaction of a metal hydride with the palladium(0), (iii) insertion of the coordinated alkene into the resulting palladium hydride, and (iv) reductive elimination between the alkyl and metal on the palladium center to release the alkylmetal species with regeneration of a palladium(0) by a reaction with alkene.