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Nonoxovanadium(IV) and Oxovanadium(V) Complexes with Mixed O, X, O-Donor Ligands (X = S, Se, P, or PO)

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Paine,  Tapan K.
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Weyhermüller,  Thomas
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Slep,  Leonardo D.
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Neese,  Frank
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Bill,  Eckhard
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Bothe,  Eberhard
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Wieghardt,  Karl
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Chaudhuri,  Phalguni
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Citation

Paine, T. K., Weyhermüller, T., Slep, L. D., Neese, F., Bill, E., Bothe, E., et al. (2004). Nonoxovanadium(IV) and Oxovanadium(V) Complexes with Mixed O, X, O-Donor Ligands (X = S, Se, P, or PO). Inorganic Chemistry, 43(23), 7324-7338. doi:10.1021/ic040052f.


Cite as: http://hdl.handle.net/21.11116/0000-0008-1082-2
Abstract
Ligating properties of four potentially tridentate bisphenol ligands containing [O, X, O] donor atoms (X = S 1, Se 2, P 3, or PO 4) toward the vanadium ions in +IV or +V oxidation states have been studied. Each ligand with different heterodonor atoms yields as expected nonoxovanadium(IV) complexes, VIVL2, whose structures have been determined by X-ray diffraction methods as having six-coordinate VIV, VO4X2, core. Compounds 1−4 have also been studied with electrochemical methods, variable-temperature (2−295 K) magnetic susceptibility measurements, X-band electron paramagnetic resonanace (EPR) (2−60 K) spectroscopy, and magnetic circular dichroism (MCD) (5 K) measurements. Electrochemical results suggest metal-centered oxidations to VV (i.e., no formation of phenoxyl radicals from the coordinated phenolates). A combination of density functional theory calculations and experimental EPR investigations indicates a dramatic effect of the heteroatoms on the electronic structure of 1−4 with consequent reordering of the energy levels; 1 and 3 possess a trigonal ground state (dz2)1, but 4 with the phosphoryl oxygen as the heterodonor atom in contrast exhibits a tetragonal ground state, (dxy)1. On the basis of the intense electronic transitions in absorption spectra, all electronic transitions observed for 4 have been assigned to ligand-to-metal charge-transfer transitions, which have been confirmed by preliminary resonance Raman measurements and C/D ratios obtained from low-temperature MCD spectroscopy. Moreover, diamagnetic complexes 5 and 6 containing mononuclear and dinuclear oxovanadium(V) units have also been synthesized and structurally and spectroscopically (51V NMR) characterized.