Principle of Highly Selective Catalytic Reactions Proceeding through Metal-Olefin Complexes

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The objective of this research project is to gain the better understanding, on the molecular level, of the highly selective catalytic reactions proceeding through metal-olefin complexes. Two primary results obtained during this research include: 1) The selectivity in the reductive elimination of -allyl(alkyl)metal complexes, which involves -olefinmetal complexes as a key intermediate, is controlled by the nature of metal (Ni)>Pd Pt) and the ancillary ligand (diphosphine monophosphine). 2) The selectivity in the transformation of the olefinmetal complexes depend on the nature of the olefin-metal bonding scheme; namely, the transformation of the -allyl(alkyl)(olefin)palladium to the C-C coupling product is enhanced by the more electron-withdrawing olefin ligand, and the transformation of the -allyl(olefin)platinum to a hydrido-platinum intermediate, a key to the catalytic olefin isomerization, is enhanced by the higher degree of olefin to metal electron donation.