om7b00593_si_002.xyz (22.65 kB)
Selective Alkene Insertion into Inert Hydrogen–Metal Bonds Catalyzed by Mono(phosphorus ligand)palladium(0) Complexes
dataset
posted on 2017-10-17, 11:34 authored by Nobuyuki Komine, Ryo Ito, Hiromi Suda, Masafumi Hirano, Sanshiro KomiyaIsolated 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.