Density functional theory study on the reductive elimination of ancillary ligand at PPC nickel complexes

Density functional theory calculations were performed to investigate the reactions between an alkyl (or aryl) substrate and a pincer ligand at the kappa(3)-PPC Ni center, where reductive elimination or H elimination reactions occur. Ni complexes with PPC-type pincer ligand showed different reactivity toward substrate, unlike conventional PCP-type ligands. For substrates lacking beta-hydrogen, reductive elimination is preferred over completing alpha-hydrogen elimination. For ethyl substrate, an intermediate and a TS for beta-H transfer with Gibbs free energy comparable to the reductive elimination were located.