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

被引：25

作者：

Fomenko, Iakov S. ^{[1
]}

Gushchin, Artem L. ^{[1
,2
]}

Abramov, Pavel A. ^{[1
,2
]}

Sokolov, Maksim N. ^{[1
,2
]}

Shul'pina, Lidia S. ^{[3
]}

Ikonnikov, Nikolay S. ^{[3
]}

Kuznetsov, Maxim L. ^{[4
]}

Pombeiro, Armando J. L. ^{[4
]}

Kozlov, Yuriy N. ^{[5
,6
]}

Shul'pin, Georgiy B. ^{[5
,6
,7
]}

机构：

[1] Russian Acad Sci, Siberian Branch, Nikolaev Inst Inorgan Chem, Dom 3, Novosibirsk 630090, Russia

[2] Novosibirsk State Univ, Ul Pirogova,Dom 2, Novosibirsk 630090, Russia

[3] Russian Acad Sci, Nesmeyanov Inst Organoelement Cpds, Ul Vavilova,Dom 28, Moscow 119991, Russia

[4] Univ Lisbon, Inst Super Tecn, Ctr Quim Estrutural, Ave Rovisco Pais, P-1049001 Lisbon, Portugal

[5] Russian Acad Sci, Dept Dynam Chem & Biol Proc, Semenov Inst Chem Phys, Ul Kosygina,Dom 4, Moscow 119991, Russia

[6] Plekhanov Russian Univ Econ, Chair Chem & Phys, Stremyannyi Pereulok Dom 36, Moscow 117997, Russia

[7] RussiaPeoples Friendship Univ Russia, Ul Miklukho Maklaya,Dom 6, Moscow 117198, Russia

来源：

CATALYSTS | 2019年 / 9卷 / 03期

基金：

俄罗斯基础研究基金会;

关键词：

oxidovanadium(IV) complexes; heterocyclic diimines; alkanes; hydrogen peroxide; alkyl hydroperoxides; DFT calculations; reaction mechanism; Fenton mechanism; SCHIFF-BASE LIGANDS; O-2-H2O2-VANADIUM DERIVATIVE-PYRAZINE-2-CARBOXYLIC ACID; H2O2-VANADIUM COMPLEX-PYRAZINE-2-CARBOXYLIC ACID; HYDROGEN-PEROXIDE; PYRAZINE-2-CARBOXYLIC ACID; VANADIUM COMPLEXES; OXOVANADIUM(IV) COMPLEXES; HYDROCARBON OXYGENATIONS; AEROBIC OXIDATION; CRYSTAL-STRUCTURE;

D O I：

10.3390/catal9030217

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页数：20