Publication Type Journal Article
Title New Oxidovanadium(IV) Complexes with 2,2 -bipyridine and 1,10-phenathroline Ligands: Synthesis, Structure and High Catalytic Activity in Oxidations of Alkanes and Alcohols with Peroxides
Authors Iakov S. Fomenko Artem L. Gushchin Pavel A. Abramov Maksim N. Sokolov Lidia S. Shul pina Nikolay S. Ikonnikov Maxim L. Kuznetsov Armando J.L. Pombeiro Yuriy N. Kozlov Georgiy B. Shul pin
Groups CCC
Journal CATALYSTS
Year 2019
Month March
Volume 9
Number 3
Pages
Abstract Reactions of [VCl3(thf)(3)] or VBr3 with 2,2-bipyridine (bpy) or 1,10-phenanthroline (phen) in a 1:1 molar ratio in air under solventothermal conditions has afforded polymeric oxidovanadium(IV) four complexes 1-4 of a general formula [VO(L)X-2](n) (L = bpy, phen and X = Cl, Br). Monomeric complex [VO(DMF)(phen)Br-2] (4a) has been obtained by the treatment of compound 4 with DMF. The complexes were characterized by IR spectroscopy and elemental analysis. The crystal structures of 3 and 4a were determined by an X-ray diffraction (XRD) analysis. The \VOBr2(bpy)\ fragments in 3 form infinite chains due to the V = O...V interactions. The vanadium atom has a distorted octahedral coordination environment. Complexes 1-4 have been tested as catalysts in the homogeneous oxidation of alkanes (to produce corresponding alkyl hydroperoxides which can be easily reduced to alcohols by PPh3) and alcohols (to corresponding ketones) with H2O2 or tert-butyl hydroperoxide in MeCN. Compound 1 exhibited the highest activity. The mechanism of alkane oxidation was established using experimental selectivity and kinetic data and theoretical DFT calculations. The mechanism is of the Fenton type involving the generation of HO center dot radicals.
DOI http://dx.doi.org/10.3390/catal9030217
ISBN
Publisher
Book Title
ISSN 2073-4344
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Conference Name
Bibtex ID ISI:000465012800011
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