Details

Autor(en) / Beteiligte

• Fomenko, Iakov S.
• Gushchin, Artem L.
• Shul’pina, Lidia S.
• Ikonnikov, Nikolay S.
• Abramov, Pavel A.
• Romashev, Nikolay F.
• Poryvaev, Artem S.
• Sheveleva, Alena M.
• Bogomyakov, Artem S.
• Shmelev, Nikita Y.
• Fedin, Matvey V.
• Shul’pin, Georgiy B.
• Sokolov, Maxim N.

Titel

New oxidovanadium( iv ) complex with a BIAN ligand: synthesis, structure, redox properties and catalytic activity

Ist Teil von

• New journal of chemistry, 2018, Vol.42 (19), p.16200-16210

Ort / Verlag

Cambridge: Royal Society of Chemistry

Erscheinungsjahr

2018

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Reaction of VCl 3 with bis[ N -(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) in air afforded [VOCl 2 (dpp-bian)] ( 1 ). The complex was characterized by IR and UV-vis spectroscopies and elemental analysis. The crystal structure of 1 was determined by X-ray diffraction (XRD) analysis. The vanadium atom is in a square-pyramidal OCl 2 N 4 coordination environment. The cyclic voltammogram (CV) in dichloromethane reveals an irreversible oxidation process at +1.40 V ( vs. Ag/AgCl) assigned to the V( iv )/V( v ) couple, and two consecutive quasi-reversible one-electron reduction processes at −0.32 V and −1.05 V ( vs. Ag/AgCl), respectively, assigned to the bian/bian −/ ˙ and bian −/ ˙/bian 2− couples, followed by irreversible reduction at −1.6 V ( vs. Ag/AgCl). The EPR spectrum of 1 in toluene shows a single 8-line signal typical for oxidovanadium( iv ) complexes with d 1 configuration. The magnetic behavior of 1 confirms the presence of one unpaired electron ( μ eff (330 K) = 1.67 μ B ), and the isolation of the paramagnetic centers. Application of 1 to oxidation of alkanes documented high catalytic activity under mild conditions. The kinetics and selectivity of alkane oxygenation by the 1 /H 2 O 2 and 1 /PCA/H 2 O 2 systems (PCA is pyrazine-2-carboxylic acid) were studied. The reaction is more efficient in the presence of PCA.