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Catalysts 2019, 9(3), 217; https://doi.org/10.3390/catal9030217

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

1
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, Prospekt Acad. Lavrentieva, dom 3, 630090 Novosibirsk, Russia
2
Novosibirsk State University, ul. Pirogova, dom 2, 630090 Novosibirsk, Russia
3
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova, dom 28, 119991 Moscow, Russia
4
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais, 1049-001 Lisboa, Portugal
5
Semenov Institute of Chemical Physics, Department of Dynamics of Chemical and Biological Processes, Russian Academy of Sciences, ul. Kosygina, dom 4, 119991 Moscow, Russia
6
Chair of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, 117997 Moscow, Russia
7
RussiaPeople’s Friendship University of Russia, ul. Miklukho-Maklaya, dom 6, 117198 Moscow, Russia
*
Authors to whom correspondence should be addressed.
Received: 24 January 2019 / Revised: 4 February 2019 / Accepted: 9 February 2019 / Published: 26 February 2019
(This article belongs to the Section Catalysis in Organic and Polymer Chemistry)
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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 14 of a general formula [VO(L)X2]n (L = bpy, phen and X = Cl, Br). Monomeric complex [VO(DMF)(phen)Br2] (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 14 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 radicals. View Full-Text
Keywords: oxidovanadium(IV) complexes; heterocyclic diimines; alkanes; hydrogen peroxide; alkyl hydroperoxides; DFT calculations; reaction mechanism; Fenton mechanism oxidovanadium(IV) complexes; heterocyclic diimines; alkanes; hydrogen peroxide; alkyl hydroperoxides; DFT calculations; reaction mechanism; Fenton mechanism
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Fomenko, I.S.; Gushchin, A.L.; Abramov, P.A.; Sokolov, M.N.; Shul'pina, L.S.; Ikonnikov, N.S.; Kuznetsov, M.L.; Pombeiro, A.J.L.; Kozlov, Y.N.; Shul’pin, G.B. 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. Catalysts 2019, 9, 217.

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