The homochiral compounds (R)- and (S)-2-diphenylphosphinoyl-2′-hydroxy-1,1′-binaphthalene, (R)- and (S)-Hbinappo, react with TiCl₄ or ZrCl₄ to produce complexes of bidentate binappo^–, [MCl₂(binappo)₂](M = Ti^IV or Zr^IV). VCl₃, FeCl₃ and MoO₂Cl₂ also react with Hbinappo, but require the presence of a base to produce [M(binappo)₃](M = V^III or Fe^III) or [MoO₂(binappo)₂]. The complex [MoO₂(acac)₂](acac = acetylacetonate) reacts with Hbinappo to produce [MoO₂(acac)(binappo)]. The vanadium(III) tris(chelate) complexes are readily oxidised in air to [VO(binappo)₂]. All of these complexes have been characterised by microanalytical, infrared, and, where appropriate, NMR, electronic and CD spectroscopic techniques. (S)-Hbinappo, [ZrCl₂{(S)-binappo}₂], [V{(S)-binappo}₃] and [VO{(S)-binappo}₂] have also been characterised by single-crystal X-ray techniques. In all of the complexes the ligands are co-ordinated through their phenolate and phosphinoyl oxygen atoms forming eight-membered chelate rings. The tris-chelate complexes form stereospecifically, (S)-binappo giving the Λ isomer exclusively, and the (R)-form producing Δ-[M(binappo)₃]. Although each of the [M(binappo)₃] species are necessarily sterically crowded, little M–O bond elongation is observed in the single-crystal X-ray structure of [V{(S)binappo}₃]. Initial attempts at achieving asymmetric induction in Ti^IV-and VO^IV-based oxidations of prochiral sulfides in the presence of these ligands are also presented, but observed enantiomeric excesses are generally < 10%.