TY - JOUR

T1 - Mononuclear Oxidovanadium(IV) Complexes with BIAN Ligands: Synthesis and Catalytic Activity in the Oxidation of Hydrocarbons and Alcohols with Peroxides

AU - Fomenko, Iakov S.

AU - Gongola, Marko I.

AU - Shul’pina, Lidia S.

AU - Ikonnikov, Nikolay S.

AU - Komarovskikh, Andrey Yu

AU - Nadolinny, Vladimir A.

AU - Kozlov, Yuriy N.

AU - Gushchin, Artem L.

AU - Shul’pin, Georgiy B.

N1 - Funding Information: Financial support from the Russian Science Foundation (grant No. 22-23-20123) and the government of the Novosibirsk region (contract r-39) is acknowledged. This work was also performed within the framework of the Program for Fundamental Research of the Russian Federation, Reg. No. 122040500068-0.; GC analysis was performed with the financial support from the Ministry of Education and Science of the Russian Federation using the equipment of the Center for Molecular Composition Studies of the A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS). The authors thank the Ministry of Science and Higher Education of the Russian Federation for access to the equipment of the Centre of Collective Usage, NIIC SB RAS (grant No. 121031700315-2). Publisher Copyright: © 2022 by the authors.

PY - 2022/10

Y1 - 2022/10

N2 - Reactions of VCl3 with 1,2-Bis[(4-methylphenyl)imino]acenaphthene (4-Me-C6H4-bian) or 1,2-Bis[(2-methylphenyl)imino]acenaphthene (2-Me-C6H4-bian) in air lead to the formation of [VOCl2(R-bian)(H2O)] (R = 4-Me-C6H4 (1), 2-Me-C6H4 (2)). Thes complexes were characterized by IR and EPR spectroscopy as well as elemental analysis. Complexes 1 and 2 have high catalytic activity in the oxidation of hydrocarbons with hydrogen peroxide and alcohols with tert-butyl hydroperoxide in acetonitrile at 50 °С. The product yields are up to 40% for cyclohexane. Of particular importance is the addition of 2-pyrazinecarboxylic acid (PCA) as a co-catalyst. Oxidation proceeds mainly with the participation of free hydroxyl radicals, as evidenced by taking into account the regio- and bond-selectivity in the oxidation of n-heptane and methylcyclohexane, as well as the dependence of the reaction rate on the initial concentration of cyclohexane.

AB - Reactions of VCl3 with 1,2-Bis[(4-methylphenyl)imino]acenaphthene (4-Me-C6H4-bian) or 1,2-Bis[(2-methylphenyl)imino]acenaphthene (2-Me-C6H4-bian) in air lead to the formation of [VOCl2(R-bian)(H2O)] (R = 4-Me-C6H4 (1), 2-Me-C6H4 (2)). Thes complexes were characterized by IR and EPR spectroscopy as well as elemental analysis. Complexes 1 and 2 have high catalytic activity in the oxidation of hydrocarbons with hydrogen peroxide and alcohols with tert-butyl hydroperoxide in acetonitrile at 50 °С. The product yields are up to 40% for cyclohexane. Of particular importance is the addition of 2-pyrazinecarboxylic acid (PCA) as a co-catalyst. Oxidation proceeds mainly with the participation of free hydroxyl radicals, as evidenced by taking into account the regio- and bond-selectivity in the oxidation of n-heptane and methylcyclohexane, as well as the dependence of the reaction rate on the initial concentration of cyclohexane.

KW - 2-pyrazinecarboxylic acid

KW - alkanes

KW - alkyl hydroperoxides

KW - BIAN ligands

KW - oxidovanadium complex

KW - oxygenation

UR - http://www.scopus.com/inward/record.url?scp=85140927679&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/35e7d6c6-d89d-31fa-bb2e-81e398f8db0c/

U2 - 10.3390/catal12101168

DO - 10.3390/catal12101168

M3 - Article

AN - SCOPUS:85140927679

VL - 12

JO - Catalysts

JF - Catalysts

SN - 2073-4344

IS - 10

M1 - 1168

ER -