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A range of unsubstituted (1,2) and 6-substituted (3–5) ortho-phenoxy-imine ligands have been prepared and converted to their silyl ether derivatives (6–10). Reaction of silyl ethers with TiCl4(thf)2 in the case of the unsubstituted species yields bis-ligated complexes while the substituted species react cleanly to yield complexes of the form [Ti(O^NR)Cl3(thf)]. In most cases the complexes have been characterised by X-ray crystallography. Testing of the complexes for ethylene oligomerisation and polymerisation has been undertaken employing alkylaluminium co-catalysts (AlEt3, MAO). In all cases the predominant product formed is polyethylene however careful analysis of the liquid phase reveals a complex process by which 1-butene is most likely formed via Cossee mechanism while 1-hexene results from a metallacyclic process.
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