Reaction of 7 equivalents of tert-butylamine with TiCl 4 in hexane at 0 ЊC gave [TiCl 2 (NCMe 3 )(NH 2 CMe 3 ) 2 ] 2 1 which on thermalisation with 2,6-diisopropylaniline in toluene gave [TiCl 2 (NC 6 H 3 Pr i 2 -2,6)(NH 2 CMe 3 ) 2 ] x 2. Imido exchange of [TiCl 2 (NCMe 3 )(NH 2 CMe 3 )] x with o-toluidine or 2-tert-butylaniline and addition of pyridine gave [TiCl 2 (NC 6 H 4 -Me-2)(py) 3 ] and [TiCl 2 (NC 6 H 4 CMe 3 -2)(py) 3 ] which crystallised to give [TiCl 2 (NC 6 H 4 Me-2)(py) 2 ] 2 3 and [TiCl 2 -(NC 6 H 4 CMe 3 -2)(py) 2 ] 2 4. 2-Phenylaniline and [TiCl 2 (NCMe 3 )(py) 3 ] gave [TiCl 2 (NC 6 H 4 Ph-2)(py) 2 ] 2 5 on crystallisation and reaction of tert-butylaniline or 2-phenylaniline with [TiCl 2 (NCMe 3 )(tmeda)] gave [TiCl 2 (NC 6 H 4 CMe 3 -2)(tmeda)] 6 and [TiCl 2 (NC 6 H 4 Ph-2)(tmeda)] 2 7. Complexes 1, 3, 4, 5, 6, and 7 were characterised by X-ray crystallography and the possibility of imdo ligand C-N bond rotation taking place analysed and compared with the NMR spectra. [TiCl 2 -(NCMe 3 )(tmeda)] and MAOؒ(MeAlO) n , polymerises ethylene at low pressure with low activity (3.2 g mmol Ϫ1 h Ϫ1 bar Ϫ1 ), [TiCl 2 (NC 6 H 4 CMe 3 )(tmeda)] or [TiCl 2 (NC 6 H 4 Ph-2)(tmeda)] and MAO gives a 4-fold increase in activity whereas propene is not polymerised but 1-hexene is. Heterogenisation by addition of [TiCl 2 (NCMe 3 )(NH 2 CMe 3 ) 2 ] 2 1 to tmeda-functionalised crosslinked polystyrene or imido exchange of [TiCl 2 (NCMe 3 )(tmeda)] with NH 2functionalised crosslinked polystyrene gives supported complexes which do not polymerise ethylene at low pressure in the presence of MAO.

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The synthesis and crystal structures of four CdII macrocyclic complexes containing mixed N-, O- and S-donors, [Cd(NO3)2([12]aneN2S2)] (1), [Cd(NO3)2([12]aneNS3)] (2), [Cd(NO3)2([15]aneNO2S2)] (3) and [Cd(NO3)([15]aneN2O2S)]NO3 (4), are presented. The metal ion is coordinated outside of the macrocyclic cavity in the complexes of the smaller macrocycles ([12]aneN2S2 and [12]aneNS3) while the flexibility of the larger macrocycles in and allows very different conformations to be adopted with a 'butterfly' geometry in and a flattened geometry in. No correlation between the number of sulfur donors and Cd-S bond distance in these types of complexes is observed, although the number and binding mode of the nitrato ligands is determined by the conformation and binding mode of the macrocycle. The position of the nitrato ligand also influences, through steric conflicts with the macrocyclic donor atoms, the bond distances in both ligand systems.