The molecular structure of 2,2'-thiobis(4-methyl-6-tert-butylphenoxy) titanium diisopropoxy (la) has been determined, The molecule exists as a dimer, in which the 1,3-dioxadititanacycle is supported by two bridging (i)Pro ligands. The coordination environment about each Ti center is best described as a distorted octahedron, where the S atom and one (i)Pro ligand occupy the axial positions, whilst two terminal phenolate and two bridging (i)Pro ligands occupy the equatorial sites, The eight-membered dioxatitanacycle adopts a symmetric-syn boat conformation, which allows for a significant sulfur-titanium interaction (S-Ti distance 2.724(2) Angstrom). A comparison between these structural features and those reported for the monomeric tetrahedral complexes 2b and 2d, where the sulfur atom is replaced by a methylene bridge in the bisphenoxy ligand, highlights the influence of the S-Ti interaction on coordination geometry, The structural features suggested for 1a to account for the higher catalytic activity of 1a/MAO in polymerization of alpha-olefins as compared with 2a/MAo are clearly demonstrated.