Ni(II) complexes bearing an o-bis(aryl)phosphinophenolate ligand were synthesized as catalysts for copolymerization of ethylene and alkyl acrylates. When the P-bound aryl group was 2,6-dimethoxyphenyl group, one of the oxygen atoms in the methoxy groups coordinated to the nickel center on its apical position. This complex was a highly active catalyst without any activators to give highly linear and high molecular weight copolymers. The structures of the copolymers were determined by H andC NMR to clarify that the alkyl acrylate comonomers were incorporated in the main chain and that the structures of the copolymers were significantly influenced by the structure of the aryl group in the ligand.

Nickel complexes bearing bidentate alkylphophine–phenolate ligands were synthesized and applied to the polymerization of propylene and the copolymerization of propylene and polar monomers. Therein, the use of bulky alkyl substituents on the phosphorus atom was crucial for the formation of highly regioregular polypropylenes. Theoretical calculations suggested that the 1,2-insertion of propylene is favored over the 2,1-insertion in these nickel-catalyzed (co)­polymerization reactions. The substituent at the ortho position relative to the oxido group greatly influences the polymerization activity, the molecular weight, and stereoregularity of the polypropylenes. This method delivers moderately isotactic ([mm] ≤ 68%) crystalline polypropylenes. The present system represents the first example for a nickel-catalyzed regiocontrolled copolymerization of propylene and polar monomers such as but-3-en-1-ol, but-3-en-1-yl acetate, and tert-butyl allylcarbamate.

Molecular orbital calculations at the ab initio level are used to study polytopal rearrangements in H2Ru(PH3)4 and H2Fe(CO)4 as models of 18-electron, octahedral metal dihydrides. It is found that, in both cases, the transition state for these rearrangements is a dihydrogen species. For H2Fe(CO)4, this is a square pyramidal complex where the H2 ligand occupies an apical position and is rotated by 45 degrees from its original orientation. This is precisely analogous to the transition state for Fe-olefin rotation in (olefin)Fe(CO)4 complexes and has a very similar electronic origin. Another transition state very close in energy is found wherein the basic coordination geometry is a trigonal bipyramid and the H2 ligand is coordinated in the axial position. For H2Ru(PH3)4, the former stationary point lies at a much higher energy and the latter clearly serves as the transition state for hydride exchange. The reason for this difference is discussed along with the roles of electron correlation in the two compounds.

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