Structural characterization of dinuclear Ti(IV) complexes of rigid tetradentate dianionic diamine bis(phenolato) ligands; effect of steric bulk on coordination features

A small difference in diamine bis(phenolato) ligands, namely an additional single methylene unit, directs formation of dinuclear Ti(IV) complexes rather than mononuclear ones as characterized by X-ray crystallography. Varying steric bulk of the ligand affects the coordination number in the dinuclear complexes and the ligand to metal ratio. A ligand with reduced steric bulk leads to a L₂Ti₂(OiPr)₄ type complex featuring two octahedral metal centers bridged only by the two phenolato ligands, whereas a bulky ligand leads to a Ti₂(μ-L¹)(μ-OiPr)₂(OiPr)₄ type complex with a single chelating ligand, two bridging isopropoxo ligands, and two terminal isopropoxo groups on each of the two metal centers, which are of trigonal bi-pyramidal geometry.