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

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. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.

Fomenko I.S.1 , Gushchin A.L.1, 2 , Abramov P.A.1, 2 , Sokolov M.N.1, 2 , Shul’pina L.S. 3 , Ikonnikov N.S. 3 , Kuznetsov M.L.4 , Pombeiro A.J.L. 4 , Kozlov Y.N.5, 7 , Shul’pin G.B. 5, 7, 6
Номер выпуска
  • 1 Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, Prospekt Acad. Lavrentieva, dom, 3, Novosibirsk, 630090, Russian Federation
  • 2 Novosibirsk State University, Ul. Pirogova, dom 2, Novosibirsk, 630090, Russian Federation
  • 3 Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Ul. Vavilova, dom 28, Moscow, 119991, Russian Federation
  • 4 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais, Lisboa, 1049‐001, Portugal
  • 5 Semenov Institute of Chemical Physics, Department of Dynamics of Chemical and Biological Processes, Russian Academy of Sciences, Ul. Kosygina, dom, 4, Moscow, 119991, Russian Federation
  • 6 People’s Friendship University of Russia, Ul. Miklukho-Maklaya, dom 6, Moscow, 117198, Russian Federation
  • 7 Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, Moscow, 117997, Russian Federation
Ключевые слова
Alkanes; Alkyl hydroperoxides; DFT calculations; Fenton mechanism; Heterocyclic diimines; Hydrogen peroxide; Oxidovanadium(IV) complexes; Reaction mechanism
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