Chemistry of hydrazonato oxovanadium(V) alkoxides derived from dihydric/monohydric alcohols

Rath, Sankar Prasad ; Mondal, Sujit ; Chakravorty, Animesh (1997) Chemistry of hydrazonato oxovanadium(V) alkoxides derived from dihydric/monohydric alcohols Inorganica Chimica Acta, 263 (1-2). pp. 247-253. ISSN 0020-1693

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The reaction of bis(acetylacetonato)oxovanadium(IV) with benzoylhydrazones of benzoylacetone and salicylaldehyde - H2babh and H2sabh, respectively - with ethane-1,2-diol (H2ed) in acetone solution has afforded the alkoxides VVO(babh)(Hed) and VVO(sabh)(Hed) in which the Hed- ligand is chelated both in the solid state and in solution. In methanol solution (no H2ed added) five-coordinated VvO(babh)(OMe) and six-coordinated VVO(sabh)(OMe)(OHMe) are formed. Aerial oxygen is the oxidant (VIV → VV) in the synthesis. The X-ray structures of VO(babh)(Hed) and VO(sabh)(OMe)(OHMe) are reported. In the VO5N coordination sphere the alcohol oxygen lies trans to the oxo oxygen. The general V---O bond length order is oxo < alkoxidic < phenoxidic < enolato < alcoholic. The complexes are mononuclear but intermolecular O---H···N hydrogen bonding afford dimers. The Hed- complexes represent authentic examples of rare oxovanadium species incorporating ethane-1,2-diol chelation uncomplicated by alkoxide bridging. The complexes have low V(V)/V(IV) reduction potentials ( E ½, -0.3 to -0.2 V) corresponding to stabilization of the pentavalent state. The methylene protons of Hed- in the complexes are inequivalent in solution (1H NMR). Crystal data: VO(babh)(Hed): monoclinic, space group P21/c, A = 11.260(6), B = 7.672(3), C = 21.072(8) Å, β = 91.95(4)°, V = 1820(1.4) Å3, Z = 4, Rw = 4.67%; VO(sabh)(OMe)(OHMe): monoclinic, space group P21/c, A = 8.170(4), B = 16.984(10), C = 12.242(7) Å, β = 104.24(4)°, V = 1646(1.6) Å3, Z = 4, R = 3.64%, Rw = 4.71%.

Item Type:Article
Source:Copyright of this article belongs to Elsevier Science.
Keywords:Oxovanadium(V) Complexes; Alkoxide Complexes; Hydrazonato Complexes; Crystal Structures
ID Code:6874
Deposited On:26 Oct 2010 05:18
Last Modified:31 Jan 2011 06:46

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