Some contribution to W(VI)-peroxo-chemistry: Synthesis,spectroscopic characterization,reactivity and DFT studies

Synthesis of white microcrystalline oxodiperoxotungstate(VI) complexes, K[WO(O₂)₂(L)(H₂O)]·H₂O, (L ?= ?salicylate, 5-chlorosalicylate, 4-hydroxybenzoate) have been achieved from reaction of Na₂WO₄·2H₂O with 30% H₂O₂ and the respective hetero-ligands at pH Ca. 7–7.5 in aqueous medium. The newly synthesized compounds were comprehensively characterized by elemental analyses, spectral studies, room temperature magnetic moment measurements and mass spectrometric studies. Infrared spectra suggest that, peroxo groups are bonded to the WO⁺⁴ center in a triangular bidentate (C_2v) fashion and the hetero-ligands benzene-core hydroxycarboxylic acids viz. salicylic acid, 5-chlorosalicylic acid, 4-hydroxybenzoic acid in anoinic form are coordinated in monodentate manner. Compounds are fairly stable in aqueous solution for sufficient period of time. The results of mass spectrometric analysis lend support to the molecular composition of the complexes ascertained on the basis of elemental analyses and spectroscopic studies. Compound potassium(aquo)(5-chlorosalicylato)oxodiperoxotungstate(VI)monohydrate, K[WO(O₂)₂(5-chlorosalicylate)(H₂O)]·H₂O, act as an oxidant of bromide ion in aqueous phase bromination of chosen organic substrates to their corresponding bromo organics. Density Functional Theory (TD-DFT) calculations were performed on the synthesized complexes substantiated the experimentally obtained results. The TD-DFT optimized structures are in excellent agreement with the results of elemental analyses, spectral as well as mass spectrometric data.