Fist oxidovanadium complexes containing chiral derivatives of dihydrophenanthroline and diazafluorene

Abstract

© 2017 Elsevier Ltd Reactions of VCl 3 with chiral derivatives of dihydrophenanthroline (2R,4R,9R,11R)-3,3,10,10-tetramethyl-1,2,3,4,6,7,9,10,11,12-decahydro-2,4:9,11-dimethanodibenzo[b,j][1,10] phenanthroline (L1) and diazafluorene (1R,3R,8R,10R)-2,2,9,9-tetramethyl-2,3,4,7,8,9,10,12-octahydro-1H-1,3:8,10-dimethanocyclopenta[1,2-b:5,4-b′]diquinoline (L2) in acetonitrile in air yield mixtures of [V III (L1/L2)(CH 3 CN)Cl 3 ] and [V IV O(L1/L2)(CH 3 CN)Cl 2 ] (I, II) which were characterized by elemental analysis, IR spectroscopy and magnetic susceptibility data. The behavior of these mixtures in different solvents was investigated by 51 V NMR and EPR spectroscopies as well as optical rotation. Recrystallization of a [V III (L1)(CH 3 CN)Cl 3 ]/[V IV O(L1)(CH 3 CN)Cl 2 ] mixture from CH 2 Cl 2 /Et 2 O affords a V(IV) complex, [V IV O(L1)(H 2 O)Cl 2 ]·nCH 2 Cl 2 (III). Recrystallization from MeOH/Et 2 O leads to complete oxidation to V(V) complex [V V O(L1)(OMe)Cl 2 ] (IV), which was characterized by X-ray crystallography, IR, 51 V and 1 H NMR spectroscopies.