Aqua Ions. 1. The structures of the [Ru(OH(2))(6)](3+) and [V(OH(2))(6)](3+) cations in aqueous solution: an EPR and UV-Vis study |
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Authors: | Dolder Stefan Spichiger David Tregenna-Piggott Philip L W |
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Institution: | Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3000, Bern 9, Switzerland. |
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Abstract: | Spectroscopic data are presented for the V(OH(2))(6)](3+) and Ru(OH(2))(6)](3+) cations, from which inferences are drawn regarding their structures in aqueous solution. EPR and absorption spectra of solutions and glasses are supplemented by spectra of the aqua ions in various crystalline environments, and the electronic and molecular structures inter-related through elementary angular overlap model calculations. It is concluded that in aqueous solution the Ru(OH(2))(6)](3+) cation is localized in the all-horizontal D(3)(d)geometry, whereas the structure of the V(OH(2))(6)](3+) cation is close to T(h) symmetry. These results are consistent with the most energetically favored geometries predicted by ab initio calculations. |
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