Metal complexes of chiral phosphorylalkoxides: crystal structure of dichlorobis[(1S)-2-(diphenylphosphoryl)-1-methylethanolato]titanium(IV)
- 1 January 1996
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 8,p. 1637-1643
- https://doi.org/10.1039/dt9960001637
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)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.Keywords
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