Metal–ligand bonding in some vanadium compounds: a study based on X-ray emission data
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 19,p. 1885-1889
- https://doi.org/10.1039/dt9750001885
Abstract
K α And KβX-ray emission spectra of V (metal), [V(pd)3](pd = pentane-2,4-dionate), VF3, VO2, V2O5, [VO][SO4], [NH4][VO3], and [NH4][V3O8] are reported. It is argued that peaks of higher energy than Kβ1,3 are due to transitions involving molecular orbitals with Vp character rather than V 3d. The relative intensities and emission energies of the Kβ1,3 , Kβ″, and Kβ2,5 peaks are discussed using m.o. theory. The Kβ″ : Kβ2,5 relative intensity is much higher than for comparable main-group compounds; this is probably due to the presence of 3p character in the orbital that gives rise to Kβ″; 3p character also enhances the intensity of Kβ2,5 . Changes in peak positions and relative intensities associated with the oxidation state of vanadium can be qualitatively rationalised by a consideration of 4p character alone. It is suggested that the Kβ‴ peak observed at higher energies (+15 eV) than Kβ2,5 is formed by relaxation of an electronically excited species (resonance radiation).Keywords
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