期刊
INORGANICA CHIMICA ACTA
卷 376, 期 1, 页码 57-63出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2011.05.033
关键词
cis-Dioxomolybdenum(VI); Oxoperoxomolybdenum(VI); Chiral Schiff base; Sulfoxidation
资金
- CSIR, India
Six new cis-dioxomolybdenum(VI) complexes of chiral Schiff-base ligands, derived from condensation of various amino alcohols and substituted salicylaldehydes, have been prepared and characterized by NMR, IR, ESI-MS and single crystal X-ray diffraction techniques. The geometry around the molybdenum center is distorted octahedral in which a tridentate Schiff-base ligand with two anionic oxygens and one neutral imine nitrogen occupies meridional position. The octahedral geometry of the cis-dioxomolybdenum center is additionally completed by a coordinated labile solvent molecule. In some complexes the sixth site is found to be vacant where the relatively bulky substituents hinder the coordination of the solvent. These complexes are tested for catalytic enantioselective sulfoxidation reactions using hydrogen peroxide as oxidant at low temperature which shows high selectivity along with good to moderate enantiomeric excess. ESI-MS study of the reaction mixture indicates the formation of oxoperoxoMo(VI) complexes during catalysis. The steric effect originated from the substituent on chiral ligand on the catalytic reaction is also discussed. It is found that the substituents at the beta position of the amino alcohol seem to greatly influence the enantioselectivity of the oxidation reactions. (C) 2011 Elsevier B.V. All rights reserved.
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