Some evidence of a dual stereodifferentiation mechanism in the polymerization of propene by alpha-diimine nickel catalysts

Nickel diimine compounds of general formula [{(ArN=C(X)C(X)=NAr)}NiBr2] (X- 2=1,8-naphthdiyl; Ar = 2,6-diisopropylphenyl, 1; 2,6-dimethylphenyl, 2; 2-i sopropyl-6-methylphenyl, 3; 2-tert-butyl-6-methylphenyl, 4; 2,4-di-tert-but yl-6-methylphenyl, 5) were synthesized and tested in the polymerization of propane to address the effects of the coordination environment at the nicke l center on the polypropylene microstructure. Compounds 1 and 2, having fou r isopropyl and four methyl ortho substituents, respectively, afford prevai lingly syndiotactic polypropylenes at -45 degreesC (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 "enantiom orphic-site" type isotactic-specific steric control opposing the syndiospec ific "chain-end" steric control. The hypothesis of a dual mechanism of ster ic 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 polypropyl ene with a low stereoregularity (rr = 33% and mm = 23%) and the latter yiel ding a prevailingly syndiotactic polymer (rr = 66%).