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

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

Результат исследования: Научные публикации в периодических изданияхстатья

9 Цитирования (Scopus)

Аннотация

Reactions of [VCl 3 (thf) 3 ] or VBr 3 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 {VOBr 2 (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 PPh 3 ) and alcohols (to corresponding ketones) with H 2 O 2 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 radicals.

Язык оригиналаанглийский
Номер статьи217
Число страниц20
ЖурналCatalysts
Том9
Номер выпуска3
DOI
СостояниеОпубликовано - 1 мар 2019

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