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Issue 19, 2018
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New oxidovanadium(IV) complex with a BIAN ligand: synthesis, structure, redox properties and catalytic activity

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Abstract

Reaction of VCl3 with bis[N-(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) in air afforded [VOCl2(dpp-bian)] (1). The complex was characterized by IR and UV-vis spectroscopies and elemental analysis. The crystal structure of 1 was determined by X-ray diffraction (XRD) analysis. The vanadium atom is in a square-pyramidal OCl2N4 coordination environment. The cyclic voltammogram (CV) in dichloromethane reveals an irreversible oxidation process at +1.40 V (vs. Ag/AgCl) assigned to the V(IV)/V(V) couple, and two consecutive quasi-reversible one-electron reduction processes at −0.32 V and −1.05 V (vs. Ag/AgCl), respectively, assigned to the bian/bian−/˙ and bian−/˙/bian2− couples, followed by irreversible reduction at −1.6 V (vs. Ag/AgCl). The EPR spectrum of 1 in toluene shows a single 8-line signal typical for oxidovanadium(IV) complexes with d1 configuration. The magnetic behavior of 1 confirms the presence of one unpaired electron (μeff (330 K) = 1.67 μB), and the isolation of the paramagnetic centers. Application of 1 to oxidation of alkanes documented high catalytic activity under mild conditions. The kinetics and selectivity of alkane oxygenation by the 1/H2O2 and 1/PCA/H2O2 systems (PCA is pyrazine-2-carboxylic acid) were studied. The reaction is more efficient in the presence of PCA.

Graphical abstract: New oxidovanadium(iv) complex with a BIAN ligand: synthesis, structure, redox properties and catalytic activity

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Publication details

The article was received on 06 Jul 2018, accepted on 27 Aug 2018 and first published on 30 Aug 2018


Article type: Paper
DOI: 10.1039/C8NJ03358G
Citation: New J. Chem., 2018,42, 16200-16210
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    New oxidovanadium(IV) complex with a BIAN ligand: synthesis, structure, redox properties and catalytic activity

    I. S. Fomenko, A. L. Gushchin, L. S. Shul’pina, N. S. Ikonnikov, P. A. Abramov, N. F. Romashev, A. S. Poryvaev, A. M. Sheveleva, A. S. Bogomyakov, N. Y. Shmelev, M. V. Fedin, G. B. Shul’pin and M. N. Sokolov, New J. Chem., 2018, 42, 16200
    DOI: 10.1039/C8NJ03358G

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