The chiral alcohols, (1S)-2-(diphenylphosphoryl)-1-methylethanol (S-Hdpomeo) and (1R)-2-(diphenylphosphoryl)-1-phenylethanol (R-Hdpopeo), have been synthesised in optically pure form by a simple two-step procedure. They can be readily deprotonated and the monoanions L so formed co-ordinate readily to Ti^IV or Mo^VI to give complexes of the type [TiCl₂L₂], cis-[MoO₂(acac)L] or cis-[MoO₂L₂]. The complex [TiCl₂(S-dpomeo)₂] crystallised in the orthorhombic space group P2₁2₁2₁, with a= 11.572(1), b= 13.209(1), and c= 20.452(1)Å. It is octahedral, with trans chlorides, and cis phosphoryl and alkoxide donors. The six-membered chelate rings adopt asymmetric boat conformations, with equatorially projecting methyl groups. This is the first structurally characterised complex containing a phosphorylalkoxide ligand. The NMR spectroscopic evidence suggests retention of the solid-state structure upon dissolution, and considerable rigidity in the chelate rings.