Metal complexes of chiral phosphorylalkoxides: crystal structure of dichlorobis[(1S)-2-(diphenylphosphoryl)-1-methylethanolato]titanium(IV)

TLDR: In this paper, the chiral alcohols, (1S)-2-(diphenylphosphoryl)-1-methylethanol (S-Hdpomeo) and (1R)-2-diphosphoryls-1-phenylethanols (R-HDPopeo), have been synthesized in optically pure form by a simple two-step procedure.

Abstract: 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 TiIV or MoVI 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)A. 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.