Synthesis of Ti(iv) complexes of donor-functionalised phenoxy-imine tridentates and their evaluation in ethylene oligomerisation and polymerisation?

Dalton Transactions Pub Date: 2013-01-29 DOI: 10.1039/C3DT32465F

Abstract

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)-C6H4C[double bond, length as m-dash]N(C(CH3)2CH2OMe) 1, 3-(adamantyl)-2-(OH)-C6H4C[double bond, length as m-dash]N(2′-(2′′-(SMe)C6H4)-C6H4) 2, 3-(t-butyl)-2-(OSiMe3)-C6H4C[double bond, length as m-dash]N(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.

Graphical abstract: Synthesis of Ti(iv) complexes of donor-functionalised phenoxy-imine tridentates and their evaluation in ethylene oligomerisation and polymerisation
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