Preparation and Characterization of Optically Active Quadridentate Schiff Base-Titanium(IV) Complexes and the Catalytic Properties of These Complexes on Asymmetric Oxidation of Methyl Phenyl Sulfide with Organic Hydroperoxides
- 1 April 1991
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 64 (4) , 1318-1324
- https://doi.org/10.1246/bcsj.64.1318
Abstract
Titanium(IV) complexes, [TiCl(Schiff base)]2O, with quadridentate Schiff base ligands derived from optically active 1,2-diamines and salicylaldehyde were prepared by treating TiCl4 with an equimolar amount of the Schiff base ligand in wet pyridine. The complexes were characterized by their 13C NMR, absorption, and circular dichroism spectra, and conductivity measurements. The complexes in dichloromethane take a μ-oxo dinuclear structure, and in methanol the complexes break up into a mononuclear species, [Ti(OMe)(MeOH)(Schiff base)]Cl. The complexes catalyze the asymmetric oxidation of methyl phenyl sulfide into the sulfoxide with organic hydroperoxides; the highest enantiomeric excess (ee) was ca. 60%. The kinetics conform to a rate law which is first order in the concentration of each sulfide, hydroperoxide, and complex catalyst.Keywords
This publication has 16 references indexed in Scilit:
- Preparation and Characterization of Optically Active Schiff Base-Oxovanadium(IV) and -Oxovanadium(V) Complexes and Catalytic Properties of These Complexes on Asymmetric Oxidation of Sulfides into Sulfoxides with Organic HydroperoxidesBulletin of the Chemical Society of Japan, 1990
- Structure of a binuclear [(1R,2R)-N,N'-disalicylidene-1,2-cyclohexanediamine]titanium(IV) complexActa Crystallographica Section C Crystal Structure Communications, 1988
- Asymmetric oxidation of sulfides mediated by chiral titanium complexes : mechanistic and synthetic aspectsTetrahedron, 1987
- Improved Optical Resolution of (±)-1,2-DiphenylethylenediamineBulletin of the Chemical Society of Japan, 1986
- A short route to chiral sulfoxides using titanium-mediated asymmetric oxidationPublished by Walter de Gruyter GmbH ,1985
- An efficient asymmetric oxidation of sulfides to sulfoxidesJournal of the American Chemical Society, 1984
- Schiff base complexes of Oxocatiohs. Part III*. Oxotitanium(IV) complexes with tetradentate optically active schiff basesInorganica Chimica Acta, 1975
- Racemization and cleavage of sulfoxides by methyllithiumJournal of the American Chemical Society, 1967
- Stereospecific Influences in Metal Complexes Containing Optically Active Ligands. Part I. Some of the Optical Isomers of Tris-(propylenediamine)-cobalt(III) IonJournal of the American Chemical Society, 1959
- Innerkomplexe TitansalzeBerichte der deutschen chemischen Gesellschaft (A and B Series), 1938