The preparation of novel titanium complexes bearing o-phosphinophenol ligands is reported. The feature of this ligand system is that its electronic and steric properties can be independently tuned. The complexes were found to be fluxional by H-1 NMR analysis at low temperature. An X-ray structural analysis showed that in the solid state the molecule is chiral at the metal center. These complexes were shown to be effective catalysts for olefin hydrogenation and imine hydrosilylation.