Beard, C.D., Barrie, R.J., Evans, J., Levason, W., Reid, G. and Spicer, M.D.
Synthesis and properties of complexes of vanadium(V) oxide trichloride with nitrogen- and oxygen-donor ligands
European Journal of Inorganic Chemistry, (21), . (doi:10.1002/ejic.200600513).
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Intensely coloured, extremely moisture sensitive complexes [VOCl3(L)] (L = pyridine, quinoline, Ph3PO, Ph3AsO, pyridine N-oxide), [VOCl3(L)(2)] (L=pyridine, Me3PO, pyridine N-oxide), [VOCl3(L-L)] [L-L = 2,2'-bipyridyl, 1,10-phenanthroline, Ph2P(O)CH2P(O)Ph-2, MeOCH2CH2OMe, 15-crown-5 or Me2NCH2CH2NMe2] and [Cl3OV(mu-L-L)VOCl3] [L-L=18crown-6 or Ph2P(O)CH2P(O)Ph-2] have been prepared from VOCl3 and the appropriate ligands in dichloromethane solution. These constitute the first extended series of complexes of vanadium(V) with neutral donor ligands. They have been fully characterised by analysis, IR, UV/Visible and multinuclear (H-1, P-31, V-51) NMR spectroscopy, and their solution behaviour probed as a function of temperature using 51V NMR spectroscopy. Reducing ligands including phosphanes, arsanes, thio- and selenoethers immediately reduce VOC13 to give V-IV or V-III species. Oxygen atom transfer reactions of some of the complexes with Ph3P, Ph3As, Me2Se and Bu2S, leading to the corresponding ligand oxides are also described.
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