NDLI: A new binuclear oxovanadium(V) complex as a catalyst in combination with pyrazinecarboxylic acid ( PCA ) for efficient alkane oxygenation by $H_{2}O

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Sutradhar, Manas Pombeiro, Armando J. L. Kozlov, Yuriy N. Guedes Da Silva, M. Fátima C. Shvydkiy, Nikita V. Kirillova, Marina V. Shul'pin, Georgiy B.
Description	Author Affiliation: Sutradhar M ( Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Technical University of Lisbon, Av. Rovisco Pais, 1049-001 Lisboa, Portugal.)
Abstract	A new binuclear oxovanadium(V) complex $[\{VO(OEt)(EtOH)\}_{2}L]$ (1) where $H_{4}L$ is bis(2-hydroxybenzylidene)terephthalohydrazide has been synthesized and fully characterized. The combination of 1 with pyrazine-2-carboxylic acid ( PCA ; a cocatalyst) affords a catalytic system for the efficient oxidation of saturated hydrocarbons , RH, with hydrogen peroxide and air in acetonitrile solution at 50 °C to produce alkyl hydroperoxides , ROOH, as the main primary products. Very high turnover numbers (TONs) have been attained in this reaction: for example, after 2220 min, TON = 44000 and initial TOF (turnover frequency) = 3300 $h^{−1}$ per molecule of complex 1. The estimated activation energy of the cyclohexane oxygenation in the presence of 1/ PCA is $E_{a}$ = 16 ± 2 kcal $mol^{−1}.$ This value is identical to that obtained for the cyclohexane oxidation with $H_{2}O_{2}$ catalyzed by the $(n-Bu_{4}N)[VO_{3}]/PCA$ combination (17 ± 2 kcal $mol^{−1}).$ The dependences of initial oxidation rates $W_{0}$ on the initial concentrations of all components of the reaction mixture have been determined. Based on these kinetic data and on the regio- and bond-selectivity parameters measured in the oxidation of linear and branched alkanes a mechanism of the oxidation has been proposed which includes the generation of hydroxyl radicals in the crucial stage.
ISSN	14779226
Issue Number	33
Volume Number	42
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-09-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Alkanes Chemistry Hydrogen Peroxide Organometallic Compounds Oxygen Pyrazinamide Analogs & Derivatives Vanadium Catalysis Hydroxyl Radical Molecular Structure Chemical Synthesis Oxidation-Reduction Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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