4.2 Article

Molybdenum(VI) complexes with tridentate Schiff base ligands derived from isoniazid as catalysts for the oxidation of sulfides: synthesis, X-ray crystal structure determination and spectral characterization

Journal

JOURNAL OF THE IRANIAN CHEMICAL SOCIETY
Volume 19, Issue 3, Pages 967-977

Publisher

SPRINGER
DOI: 10.1007/s13738-021-02355-0

Keywords

Molybdenum; Crystal structure; ONO-tridentate Schiff base; Homogeneous catalyst

Funding

  1. Ardakan University

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Two new molybdenum complexes have been synthesized and characterized spectroscopically, with their solid-state structures confirmed by single-crystal X-ray diffraction. These complexes exhibit efficient catalytic activity in oxidizing sulfides, demonstrating high yield, short reaction time, and excellent selectivity in producing sulfoxides.
Two new complexes, including [MoO2(L-1)(CH3OH)] and [MoO2(L-2)(CH3OH)], with tridentate ONO-donor Schiff base ligands (H2L1: (E)-N'-(2-hydroxy-3-methoxybenzylidene)isonicotinohydrazide and H2L2: (E)-N'-(5-chloro-2-hydroxybenzylidene)isonicotinohydrazide) have been synthesized and characterized spectroscopically through FT-IR and H-1-NMR and by elemental analyses. Their solid-state structures were also confirmed by single-crystal X-ray diffraction (SC-XRD) technique. These tridentate Schiff base ligands coordinated to the metal ion via phenolate oxygen, imine nitrogen and enolic oxygen atoms. In the complexes, the molybdenum center adapts a slightly distorted octahedral geometry, by using three O,N,O-donor atoms of the tridentate ligands, methanol and an oxo group employing the axial positions, while another oxo group makes the equatorial plane. Moreover, the complexes were utilized in oxidizing the different sulfides as an efficient homogeneous catalyst in the presence of tert-butyl hydroperoxide (TBHP) as an oxidizing agent in 1,2-dichloroethane (DCE) as a solvent under refluxed conditions. This method has numerous ascendancies such as high yield, short reaction time and excellent selectivity to produce corresponding sulfoxides without overoxidation to sulfones.

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