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Oxidation of sulfides including DBT using a new vanadyl complex of a non‐innocent o ‐aminophenol benzoxazole based ligand
Author(s) -
Saeedi Roonak,
Safaei Elham,
Lee YongIll,
Lužnik Janez
Publication year - 2019
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.4781
Subject(s) - chemistry , benzoxazole , ligand (biochemistry) , electron paramagnetic resonance , thioether , moiety , dibenzothiophene , octahedron , medicinal chemistry , catalysis , octahedral molecular geometry , photochemistry , electrochemistry , inorganic chemistry , crystal structure , crystallography , stereochemistry , organic chemistry , biochemistry , physics , receptor , electrode , nuclear magnetic resonance
Reaction of a non‐innocent o ‐aminophenol benzoxazole based ligand HL BAP with VOCl 3 afforded a vanadyl complex, VOL BIS (SQ), in which SQ is a 2,4‐di‐ tert ‐butylsemiquinone produced from hydrolysis of HL BAP . The crystal structure of VOL BIS (SQ) exhibits an octahedral geometry with the VO 2+ center coordinated by two nitrogen and one oxygen atoms of L BAP and two oxygen atoms of SQ. Electrochemical studies showed quasi‐reversible metal‐centered reduction and ligand‐centered oxidation of complex. The magnetic moment of VOL BIS (SQ) is consistent with the spin‐only value expected for S = 1/2 system. The neutral species of VOL BIS (SQ) is EPR active, which is consistent with a paramagnetic electronic ground state ( S = 1/2). This result is in accordance with the vanadyl (IV) moiety surrounded by tridentate iminobenzosemiquinonate anion radical (HL BIS ) •‐ and benzosemiquinone ligand (SQ) • . The theoretical calculations confirm the experimental results. Furthermore, we present the optimal conditions for maximum efficiency of sulfide oxidation for oxidative desulfurization with hydrogen peroxide and 6 times reusability of catalyst for sulfoxidation of dibenzothiophene.