Substituent effects in (kappa(2)-N,O)-salicylaldiminato nickel(II)-methyl pyridine polymerization catalysts: Terphenyls controlling polyethylene microstructures

作者：Goettker Schnetmann Inigo; Wehrmann Peter; Roehr Caroline; Mecking Stefan^*

来源：Organometallics, 2007, 26(9): 2348-2362.

DOI：10.1021/om0611498

A series of (kappa(2)-N,O)-salicylaldiminato Ni(II)-methyl pyridine complexes 7-pyr and 8-pyr derived from 3,5-diiodosalicyaldehyde (3a) and 3-(9-anthryl)salicylaldehyde (3b), and terphenylamines 2,6-(3,5-R-4-R'-C6H2)(2)C6H3-NH2 (4a, R = CF3, R' = H; 4b, R = Bu-t, R' = H; 4c, R = Bu-t, R' = OH; 4d, R = Me, R' = H; 4e, R = Me, R' = MeO; 4f, R = MeO, R' = H; 4g, R = MeO, R' = MeO), was prepared by reaction of the respective salicylaldimine (5a-BOBO-f, 6a-g) with [(tmeda)Ni(CH3)(2)] (tmeda = N,N,N',N'-tetramethylethylenediamine) or [(pyridine)(2)Ni(CH3)(2)]. Complexes 7-pyr and 8-pyr are highly active single component catalysts for the polymerization of ethylene, producing a wide range of different polyethylene microstructures. While comparable complexes derived from 3a, 3b, 5-nitrosalicylaldehyde, 3-tert-butylsalicylaldehyde, 3,5-[3,5-(CF3)(2)C6H3](2)-salicylaldehyde, and 2,6-[3,5-(CF3)(2)C6H3](2)C6H3-NH2 afford polyethylenes with similar degrees of branching, variation of the terphenyl moieties in complexes 7-pyr and 8-pyr allows access to a wide range of polyethylene microstructures under identical reaction conditions. The X-ray diffraction analyses of complexes 7b-pyr and 8f-pyr are reported.

• 出版日期2007-4-23