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A number of analogues of the Mitsui Chemicals ethylene trimerisation system (IV) have been explored, in which one of the donor atoms have been modified. Thus, a series of mono-anionic tridentate phenoxy-imine (3-(t-butyl)-2-(OH)-C6H4CN(C(CH3)2CH2OMe) 1, 3-(adamantyl)-2-(OH)-C6H4CN(2′-(2′′-(SMe)C6H4)-C6H4) 2, 3-(t-butyl)-2-(OSiMe3)-C6H4CN(C(CH3)2CH2OMe) 3) or phenoxy-amine (3,5-di(t-butyl)-2-(OH)-C6H4CH2-N(2′-(2′′-(OMe)C6H4)-C6H4) 4) ligands have been prepared and reacted with TiCl4 or TiCl4(thf)2 to give the mono-ligand complexes 5–7. The solid state structures of compounds 4–6 have been determined. Complexes 5–7 have been tested for their potential as ethylene oligomerisation/polymerisation systems in conjunction with MAO activator and benchmarked against the Mitsui phenoxy-imine trimerisation system IV. While the phenoxy-amine complex 6 shows a propensity for polymer formation, the phenoxy-imine complexes 5 and 7 show somewhat increased formation of short chain LAOs. Complex 5 is selective for 1-butene in the oligomeric fraction, while 7 displays liquid phase selectivity to 1-hexene. As such 7, which is a sulfur substituted analogue of the Mitsui system IV, displays similar characteristics to the parent catalyst. However, its utility is limited by the lower activity and predominant formation of polyethylene.
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