Some Evidence of a Dual Stereodifferentiation Mechanism in the Polymerization of Propene by α-Diimine Nickel Catalysts

Nickel diimine compounds of general formula [{(ArN C(X)C(X) NAr)}NiBr 2 ] (X 2 = 1,8-naphthdiyl; Ar = 2,6-diisopropylphenyl, 1; 2,6-dimethylphenyl, 2; 2-isopropyl-6-methylphenyl, 3; 2- tert -butyl-6-methylphenyl, 4; 2,4-di- tert- butyl-6-methylphenyl, 5 ) were synthesized and tested in the polymerization of propene to address the effects of the coordination environment at the nickel center on the polypropylene microstructure. Compounds 1 and 2, having four isopropyl and four methyl ortho substituents, respectively, afford prevailingly syndiotactic polypropylenes at −45 °C (rr = 75% for 1 and rr = 61% for 2 ) through a “chain-end” control mechanism. Compounds such as 3, 4, and 5, having two different ortho substituents on the same aromatic ring, can exist as either rac or meso isomers. Rac - 3 and rac - 4 afford much less stereoregular polypropylenes with respect to 1 and 2 (e.g., mm = 41% and rr = 25% for rac - 3) . These C 2 -symmetric catalysts could provide an “enantiomorphic-site” type isotactic-specific steric control opposing the syndiospecific “chain-end” steric control. The hypothesis of a dual mechanism of steric control being operative has been supported by the synthesis of both the rac and the meso isomers of 5, with the former still affording a polypropylene with a low stereoregularity (rr = 33% and mm = 23%) and the latter yielding a prevailingly syndiotactic polymer (rr = 66%).