Influence of the metal centers of 2,6-bis(imino)pyridyl transition metal complexes on ethylene polymerization/oligomerization catalytic activities

Much work on bis(imino)pyridyl complexes with Fe(II) and Co(II) as ethylene polymerization catalysts has been reported in terms of designing new analogous ligands, while little work has been dedicated to the study of the effect of the metal center on catalyst performance. A series of bis(imino)pyridyl-MCl2 (M = Fe(II), Cu(II), Ni(II), Cu(II), Zn(II)) transition metal complexes were synthesized, for which single crystals of the Co(II) and Cu(II) complexes were obtained. The crystal structures indicated that these complexes had similar coordination geometries. Being applied to ethylene polymerization at 25 degrees C and employing 500 equiv. of methylaluminoxane as co-catalyst, the complexes with Fe(II), Co(II) and Ni(II) centers showed, respectively, catalytic activities of 1.25 x 10(6) g (mol Fe)(-1) h(-1) Pa for ethylene polymerization, and 3.98 x 10(5) g (mol Co)(-1) h(-1) Pa and 5.13 x 10(3) g (mol Ni)(-1) h(-1) Pa for ethylene oligomerization. In contrast, the complexes with Cu(II) and Zn(II) centers were inactive. Crystal structure data showed that the coordination interactions provided a comparatively reliable quantification of the selectivity of the bis(imino)pyridyl ligand for the studied metal ions, which was in reasonable agreement with the Irving-Williams list. Moreover, for the Ni(II) and Cu(II) complexes, the strong coordination bonds and small N(imino)-M-N(imino) angles were unfavorable for several steps in the mechanism, such as ethylene coordination to the metal center, ethylene migratory insertion and olefin chain growth. All of these will reduce the speed of the overall reaction, indicating a decrease of catalytic efficiency in a given period. The poor activity of the Zn(II) complex for ethylene polymerization may be related to the reduction process by the alkylating agent. (C) 2010 Society of Chemical Industry