Computational Study of Reduction Potentials of Th(4+) Compounds and Hydrolysis of ThO2(H2O)n, n = 1, 2, 4.


Gorden, AE; McKee, ML; (2016) Computational Study of Reduction Potentials of Th(4+) Compounds and Hydrolysis of ThO2(H2O)n, n = 1, 2, 4. The journal of physical chemistry A. ISSN 1089-5639 DOI: https://doi.org/10.1021/acs.jpca.6b08472

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Abstract

The stability of Th(4+) to reduction in water is studied by DFT methods. The standard reduction potential (SRP) of homoleptic complexes including Th(H2O)9(4+), Th(H2O)10(4+), Th(NO3)4, Th(NO2)6(2-), Th(NO3)6(2-), Th(COT)2, Th(acac)4, ThCp4, ThF4, and ThCl4 have been investigated. The values vary widely (from -3.50 V for Th(OH)4 to -0.62 V for Th(NO3)4 depending on whether the ligands are redox active (noninnocent) or not. Several additional topics of thorium chemistry are explored, including the hydrolysis mechanism of ThO2(H2O)n, n = 1, 2, 4, and the solution phase nonzero dipole moment of ThCp4. Dinuclear complexes are also characterized, including Th2O4, Th2O2(OH)4, Th2O2(H2O)8, Th2(OH)8(H2O)4, and Th2(OH)2(NO3)6(H2O)4 and condensed thorium complexes as [Th4(OH)6(H2O)12](10+) and [Th6(OH)14(H2O)12](10+). For the Th2(OH)2(NO3)6(H2O)4 dinuclear complex, the first SRP is -0.82 V and the second is 1.59 V. The first SRP corresponds to the reduction of the ligand NO3(-), and the second SRP corresponds to dissociative electron transfer to the NO3(2-) ligand. The calculated formation constant of Th(EDTA)(H2O)4 is in reasonable agreement with experiment. The different stereochemistries of the bidentate ligands NO2(-), NO3(-), and acetylacetonate (acac) around the thorium center have very similar stabilities.

Item Type: Article
Faculty and Department: Faculty of Public Health and Policy > Dept of Health Services Research and Policy
PubMed ID: 27712072
URI: http://researchonline.lshtm.ac.uk/id/eprint/2965083

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