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• W2086486495 abstract "In the title family, the ONO donor ligands are the acetylhydrazones of salicylaldehyde (H2L1) and 2-hydroxyacetophenone (H2L2) (general abbreviation, H2L). The reaction of bis(acetylacetonato)oxovanadium(IV) with a mixture of tridentate H2L and a bidentate NN donor [e.g., 2,2′-bipyridine(bpy) or 1,10-phenanthroline(phen), hereafter B] ligands in equimolar ratio afforded the tetravalent complexes of the type [VIVO(L)(B)]; complexes (1)–(4) whereas, if B is replaced by 8-hydroxyquinoline(Hhq) (which is a bidentate ON donor ligand), the above reaction mixture yielded the pentavalent complexes of the type [VVO(L)(hq)]; complexes (5) and (6). Aerial oxygen is most likely the oxidant (for the oxidation of VIV → VV) in the synthesis of pentavalent complexes (5) and (6). [VIVO(L)(B)] complexes are one electron paramagnetic and display axial EPR spectra, while the [VVO(L)(hq)] complexes are diamagnetic. The X-ray structure of [VVO(L2)(hq)] (6) indicates that H2L2 ligand is bonded with the vanadium meridionally in a tridentate dinegative fashion through its phenolic-O, enolic-O and imine-N atoms. The general bond length order is: oxo < phenolato < enolato. The V–O (enolato) bond is longer than V–O (phenolato) bond by ∼0.07 Å and is identical with V–O (carboxylate) bond. 1H NMR spectrum of (6) in CDCl3 solution indicates that the binding nature in the solid state is also retained in solution. Complexes (1)–(4) display two ligand-field transitions in the visible region near 820 and 480 nm in DMF solution and exhibit irreversible oxidation peak near +0.60 V versus SCE in DMSO solution, while complexes (5) and (6) exhibit only LMCT band near 535 nm and display quasi-reversible one electron reduction peak near −0.10 V versus SCE in CH2Cl2 solution. The VO3+–VO2+ E1/2 values shift considerably to more negative values when neutral NN donor is replaced by anionic ON donor species and it also provides better VO3+ binding via phenolato oxygen. For a given bidentate ligand, E1/2 increases in the order: (L2)2− < (L1)2−." @default.
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• W2086486495 date "2005-03-01" @default.
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• W2086486495 title "Synthesis, structure and solution chemistry of mixed-ligand oxovanadium(IV) and oxovanadium(V) complexes incorporating tridentate ONO donor hydrazone ligands" @default.
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• W2086486495 doi "https://doi.org/10.1016/j.ica.2004.11.015" @default.
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