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From Symmetrical to Unsymmetrical Bimetallic Nickel Complexes Bearing Aryl-linked Iminopyridines; Synthesis, Structures and Ethylene Polymerisation Studies by Jérémie D.A. Pelletier; John Fawcett; Kuldip Singh; Gregory A. Solan is a Chemistry article available to read on EtoBox.

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Both symmetrical and unsymmetrical tetramethylphenyl-linked iminopyridines, 1,4-{(2-C 5 H 4 N)RC@N} 2 -2,3,5,6-Me 4 C 6 [R = H (L1a), Me (L1b)] and 1-{(2-C 5 H 4 N)HC@N}-4-{(2-C 5 H 4 N)MeC@N}-2,3,5,6-Me 4 C 6 (L1c), have been prepared in good yield using straightforward condensation strategies. The molecular structures of L1a and L1c reveal the adjacent imino and pyridyl nitrogen atoms to adopt transoid configurations. Interaction of L1x with two equivalents of NiX 2 in moderate to good yield. Adduct formation results on treatment of bromide-containing 1a-1c with DMF (dimethylformamide) to yield dicationic [(L1x)Ni 2 Br 2 (DMF) 6 ]Br 2 [L1x = L1a (2a), L1b (2b), L1c (2c)], while with chloride-containing 1d the neutral species [(L1a)Ni 2 Cl 4 (DMF) 4 ] (3) is obtained. Activation of 1a-1d and 2c with excess methylaluminoxane (MAO) generates active ethylene polymerisation catalysts (1b/MAO > 1c/MAO > 1a/MAO $ 1d/MAO > 2c/MAO) affording mixtures of waxes and low molecular weight solid polyethylene. Multinuclear NMR and GC analysis of the waxy components reveal methyl branched materials that contain mostly internal unsaturation along with low levels of a-olefins. Broad molecular weigh

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Author

Jérémie D.A. Pelletier; John Fawcett; Kuldip Singh; Gregory A. Solan

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 0022-328X)

Published

2008

Language

EN

Field

Chemistry (Physical Sciences)