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Reaction of Me4DACH (6-dimethylamino-1,4,6-trimethyl-1,4-diazacycloheptane) with Ti(NtBu)Cl2(py)3 or Ti(NtBu)Cl2(NHMe2)2 gave Ti(NtBu)(Me4DACH)Cl2 (1) which in CD2Cl2 solution exists as a mixture of trans and cis isomers (defined with respect to the imido ligand and the exocyclic NMe2 donor of Me4DACH). Aryl imido analogues of 1 were prepared from Ti(NAr)Cl2(NHMe2)2 and Me4DACH forming Ti(NAr)(Me4DACH)Cl2 (Ar = 2,6-C6H3Me2 (2), 2,6-C6H3iPr2 (3), 2-C6H4tBu (4), 2-C6H4CF3 (5)) which also exist as isomers in solution. The activation parameters for the interconversion of trans- and cis-3 were measured by VT NMR spectroscopy. The solid state structures of trans-1, 3 and 4 and cis-2 have been determined. In the presence of MAO or dried MAO the compounds 1–5 act as moderatley productive ethylenepolymerisationcatalysts, with a modest productivity gain found on moving from the 1/MAO to 1/dried MAOcatalyst system.
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