Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

ENDOR-determined solvation structure of VO/sup 2 +/ in frozen solutions

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00292a020· OSTI ID:6181224
The solvation structure of the vanadyl ion (VO/sup 2 +/) in methanol and in water-methanol mixtures has been investigated by application of /sup 1H/ and /sup 13/C electron nuclear double resonance (ENDOR) spectroscopy. The ligand origins of the proton ENDOR resonances have been assigned with use of materials selectively enriched with /sup 2/H. The principal hyperfine coupling (hfc) components of both /sup 1/H and /sup 13/C in solvent molecules coordinated to the VO/sup 2 +/ ion have been determined by analysis of the H/sub 0/ dependence of the ENDOR spectra. The ENDOR results provide unambiguous evidence that in water-methanol mixtures only VO(H/sub 2/O)/sub 5//sup 2 +/ and (VO(H/sub 2/O)/sub 4/(CH/sub 3/OH))/sup 2 +/ species are formed. In pure methanol the VO(CH/sub 3/OH)/sub 5//sup 2 +/ species is observed. The coordination geometries of the VO/sup 2 +/ complexes are deduced from ENDOR estimates of metal-nucleus distances by using computer-based molecular graphics. It is shown on the basis of molecular modeling that the ENDOR-determined metal-nucleus distances are best accounted for by complexes of tetragonal-pyramidal geometry. 29 references, 9 figures, 7 tables.
Research Organization:
Univ. of Chicago, IL (USA)
OSTI ID:
6181224
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:19; ISSN INOCA
Country of Publication:
United States
Language:
English