Solution study of a structurally characterized monoalkoxo-bound monooxo-vanadium(V) complex: spontaneous generation of the corresponding oxobridged divanadium(V,V) complex and its electroreduction to a mixed-valence species in solution.
An interesting transformation of a structurally characterized monooxoalkoxovanadium(V) complex [VO(OEt)L] (LH 2 = a dibasic tridentate ONO donor ligand) in solution leading to the formation of the corresponding monooxobridged divanadium(V,V) complex (VOL) 2O is reported. This binuclear species in solution is adequately characterized by elemental analysis, measurement of conductance (in solution), various spectroscopic (UV-vis, IR, NMR, and mass spectrometry) techiniques and by cyclic voltammetry. The corresponding mixed-valence vanadium(IV,V) species has been generated in CH 3CN solution by controlled potential electrolysis of (VOL) 2O. This mixed-valence species is identified and studied by EPR technique (at room temperature and at liquid nitrogen temperature) and also by UV-vis spectroscopy. This study may be regarded as a general method of obtaining monooxo-bridged binuclear vanadium(V,V) species from the corresponding mononuclear monooxoalkoxovanadium(V) complexes of some selected dibasic tridentate ONO chelating ligands, which can be utilized as the precursor of monooxobridged divanadium(IV,V) mixed-valence species in solution obtainable by controlled potential electrolysis.
Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700 032, India.
Rupam
R
Dinda
Parbati
P
Sengupta
Manas
M
Sutradhar
Thomas C W
TC
Mak
Saktiprosad
S
Ghosh
D004563:Electrochemistry; D004572:Electrolysis; D004578:Electron Spin Resonance Spectroscopy; D010084:Oxidation-Reduction; D012996:Solutions; D013057:Spectrum Analysis; D014638:Vanadates / Q000737:chemistry*
D012996:Solutions; D014638:Vanadates