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Issue 20, 2002
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Conformational changes of an oxovanadium complex probed by ENDOR spectroscopy and DFT calculations

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Abstract

An angular selective ENDOR study, in combination with DFT calculations, was used to investigate the structure and conformational changes of the bis(acetylacetonato)-oxovanadium(IV) complex ([VIV[double bond, length half m-dash]O(acac)2]) in frozen solution. In the presence of a non-coordinating solvent (dichloromethane), both ENDOR analysis and DFT calculations confirm the expected square pyramidal structure of the complex. However, when a strongly coordinating solvent (d5-pyridine) was used, different structural isomers of the resulting ([VIV[double bond, length half m-dash]O(acac)2(C5D5N)]) adduct were found to co-exist in the frozen solution. ENDOR simulations indicate that 60% of the adduct is present as the cis-isomer, while 40% is present as the trans-isomer. The ligand coordinates of both isomers, as determined by ENDOR spectroscopy, were in excellent agreement with the optimised structure based on DFT calculations. In addition, the DFT calculations showed that the total energy of the two isomers for the pyridine case differ by only 3 kJ mol−1, in agreement with the experimentally observed equilibrium mixture containing both isomers.

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Article information


Submitted
10 May 2002
Accepted
23 Aug 2002
First published
16 Sep 2002

Phys. Chem. Chem. Phys., 2002,4, 4937-4943
Article type
Paper

Conformational changes of an oxovanadium complex probed by ENDOR spectroscopy and DFT calculations

D. M. Murphy, I. A. Fallis, R. D. Farley, R. J. Tucker, K. L. Avery and D. J. Willock, Phys. Chem. Chem. Phys., 2002, 4, 4937
DOI: 10.1039/B204564H

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