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Non-symmetric diimine ligands (Ar-N=C(CH 3 )-(CH 3 )C=NAr*; Ar: 2,6-diisopropyl-phenyl; Ar*: 2,6-di(4-tert-butyl-phenyl)phenyl (4b), 2,6-di(4-OCH 3 )-phenyl)phenyl (4c)) were synthesized and converted in-situ into the corresponding nickel dibromo complexes (5b, c) by reaction with (DME)NiBr 2 . The complexes were activated for ethene polymerization by treatment with MAOat ambient temperature. The resulting highmolecular weight polymer products (M W  &gt; 4.0 x 10 6  g mol -1 ) have a branched microstructure (predominantly methyl groups), as indicated by  13 C NMR spectroscopy. The degree of branching can be controlled by a proper choice of the 2,6-diphenyl modified aniline moieties resulting in melting transitions ranging from 92 - 130 °C.

Novel Non-Symmetric Nickel-Diimine Complexes for the Homopolymerization of Ethene: Control of Branching by Catalyst Design