The chloro-tris-phenoxo complexes [TiCl(OAr) 3 ] (OAr=OC 6 H 4 CMe 3 -4 (1), OC 6 H 3 Me 2 -2,4 (2), OC 6 H 2 Me 3 -2,4,6 (4), OC 6 H 3 (CHMe 2 ) 2 -2,6 (5), OC 6 H 3 (CMe 3 ) 2 -2,4 (6) and OC 6 H 4 Ph-2 (8) are prepared by heating 3 equivalents of the phenol and [TiCl 4 ] in toluene. X-ray crystal structure determinations show that 2 is a phenoxy-bridged dimer with the ortho-methyl groups making the beginning of a pocket about the terminal chloro ligand and 6 is a tetrahedral monomer in which the pocket is more well developed by the ortho-tert-butyl groups. Both 2 and 6 react with dmbipy to give [TiCl(OAr) 3 (dmbipy)] [OAr=OC 6 H 3 Me 2 -2,4 (3) and OC 6 H 3 (CMe 3 ) 2 -2,4 (7)] in which the original pocket is destroyed. Reaction of TiCl 4 with 3 equivalents of LiOC 6 H 4 Ph-2 in diethyl ether gives [TiCl(OC 6 H 4 Ph-2) 3 (diethyl ether)] (9) for which an X-ray crystal structure determination shows a trigonal bipyramidal coordination geometry with the diethyl ether lying trans to the chloro ligand. The three phenoxide ligands make up the equatorial plane which takes the 2-phenyl substituent on each phenoxo ligand away from the chloro ligand resulting in a partially collapsed cavity. The tied-back analogues of 2 and 6, [TiCl{(OC 6 H 2 Me 2 -2,4-CH 2 -6) 3 N}] (11) and [TiCl({OC 6 H 2 (CMe 3 ) 2 -2,4-CH 2 -6} 3 N)]·diethyl ether (12), are prepared by adding (HOArCH 2 ) 3 N [Ar=C 6 H 2 Me 2 -2,4 and C 6 H 2 (CMe 3 ) 2 2,4] to [TiCl(OCHMe 2 ) 3 ] in diethyl ether. An X-ray crystal structure of 12 showed a trigonal bipyramidal structure with a coordination environment about the terminal chloro ligand similar to that found in 6. Complex 12 reacts with pyridine to form the 6-coordinate complex [TiCl({OC 6 H 2 (CMe 3 ) 2 -2,4-CH 2 -6} 3 N)(py)] (13).