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Structure and Bonding of the vanadium(III) Hexa-Aqua Cation. 1. Experimental Characterization and Ligand-Field Analysis

Structure and Bonding of the vanadium(III) Hexa-Aqua Cation. 1. Experimental Characterization and Ligand-Field Analysis

Philip L W Tregenna-Piggott, David Spichiger, Graham Carver, Beatrice Frey, Roland Meier, Høgni Weihe, John A Cowan, Garry J McIntyre, Gernot Zahn, Anne-Laure Barra

Inorg Chem. 2004 Dec 13;43(25):8049-60.

PMID: 15578844

Abstract:

Spectroscopic and crystallographic data are presented for salts containing the [V(OH(2))(6)](3+) cation, providing a rigorous test of the ability of the angular overlap model (AOM) to inter-relate the electronic and molecular structure of integer-spin complexes. High-field multifrequency EPR provides a very precise definition of the ground-state spin-Hamiltonian parameters, while single-crystal absorption measurements enable the energies of excited ligand-field states to be identified. The EPR study of vanadium(III) as an impurity in guanidinium gallium sulfate is particularly instructive, with fine-structure observed attributable to crystallographically distinct [V(OH(2))(6)](3+) cations, hyperfine coupling, and ferroelectric domains. The electronic structure of the complex depends strongly on the mode of coordination of the water molecules to the vanadium(III) cation, as revealed by single-crystal neutron and X-ray diffraction measurements, and is also sensitive to the isotopic abundance. It is shown that the AOM gives a very good account of the change in the electronic structure, as a function of geometric coordinates of the [V(OH(2))(6)](3+) cation. However, the ligand-field analysis is inconsistent with the profiles of electronic transitions between ligand-field terms.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP13494912	Gallium(III) sulfate		13494-91-2	Price

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