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Peroxo–tungstate(VI) complexes: syntheses, characterization, reactivity, and DFT studies

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Abstract

Three new oxodiperoxo–tungsten(VI) complexes containing benzene core carboxylic acids, viz., benzoic acid, 2-chlorobenzoic acid, and 3-aminobenzoic acid as co-ligands have been synthesized from reaction of Na2WO6H4, 30% H2O2 and the corresponding co-ligands in aqueous medium. The compounds have been comprehensively characterized by elemental analyses, FT-IR, 1H NMR, UV–Vis spectral studies as well as by mass spectrometric and TGA analyses. The infrared spectra suggest occurrence of terminally bonded W=O as well as triangular bidentate peroxo groups (C2v) and monodentate carboxylate group bound to the WO4+ center. The mass spectra of the compounds are in good agreement with proposed molecular formulations. Thermogravimetric analyses indicate the existence of both lattice and coordinated water molecules in the complexes. Density functional theory (DFT) calculations were used to compute the frequencies of relevant vibrational modes, electronic properties and also to investigate structure of the compounds. Compound potassium(aquo)(2-chlorobenzoato)oxodiperoxo–tungstate(VI)dihydrate acts as an oxidant for bromide ion in aqueous phase bromination of chosen organic substrates to their corresponding bromo-organics.

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Acknowledgements

The authors are thankful to Tripura University for providing the infrastructure facilities; Prof. A. Saikia, Department of Chemistry, I.I.T Guwahati, for cooperation in recording of mass spectra. N. D is grateful to Tripura University for award of research fellowship (No. F.TU/ REG/Ph.D/(Admn)/01/12) RET (UGC, New Delhi, India, sponsored). Authors are thankful to DST, Govt. of India, for providing 400 MHz NMR spectrometer to Tripura University under Fist program (SR/FST/CSI-263/2015). We are thankful to esteemed reviewers for helpful comments at the stage of revision.

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Authors and Affiliations

  1. Department of Chemistry, Tripura University, Suryamaninagar, Tripura, 799022, India

    Nandita Das & Ranendra N. Dutta Purkayastha

  2. Department of Chemistry, University of Gour Banga, Malda, West Bengal, 732103, India

    Shubhamoy Chowdhury

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  1. Nandita Das
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Correspondence to Ranendra N. Dutta Purkayastha.

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706_2019_2435_MOESM1_ESM.docx

Experimental IR spectra, UV-Vis spectra, mass spectra, TGA plot, and NMR spectra, Table for selected optimized bond angles and bond lengths. Supplementary file1 (DOCX 3337 kb)

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Das, N., Chowdhury, S. & Purkayastha, R.N.D. Peroxo–tungstate(VI) complexes: syntheses, characterization, reactivity, and DFT studies. Monatsh Chem 150, 1255–1266 (2019). https://doi.org/10.1007/s00706-019-02435-1

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