TY - JOUR

T1 - New oxidovanadium(iv) complex with a BIAN ligand

T2 - synthesis, structure, redox properties and catalytic activity

AU - Fomenko, Iakov S.

AU - Gushchin, Artem L.

AU - Shul'pina, Lidia S.

AU - Ikonnikov, Nikolay S.

AU - Abramov, Pavel A.

AU - Romashev, Nikolay F.

AU - Poryvaev, Artem S.

AU - Sheveleva, Alena M.

AU - Bogomyakov, Artem S.

AU - Shmelev, Nikita Y.

AU - Fedin, Matvey V.

AU - Shul'pin, Georgiy B.

AU - Sokolov, Maxim N.

N1 - Publisher Copyright: © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

PY - 2018/10/7

Y1 - 2018/10/7

N2 - 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.

AB - 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.

KW - O-2-H2O2-VANADIUM DERIVATIVE-PYRAZINE-2-CARBOXYLIC ACID

KW - DIIMINE NI(II) CATALYST

KW - HYDROGEN-PEROXIDE

KW - COMPLEX-PYRAZINE-2-CARBOXYLIC ACID

KW - PYRAZINE-2-CARBOXYLIC ACID

KW - VANADIUM COMPLEXES

KW - HYDROCARBON OXYGENATIONS

KW - PYRAZINECARBOXYLIC ACID

KW - COORDINATION CHEMISTRY

KW - ELECTRONIC-STRUCTURE

UR - http://www.scopus.com/inward/record.url?scp=85054014740&partnerID=8YFLogxK

U2 - 10.1039/C8NJ03358G

DO - 10.1039/C8NJ03358G

M3 - Article

AN - SCOPUS:85054014740

VL - 42

SP - 16200

EP - 16210

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 19

ER -