Computational Study of Reduction Potentials of Th4+ Compounds and Hydrolysis of ThO2 (H2O) n, n= 1, 2, 4

Anne Gorden, Michael L McKee

Research output: Contribution to journalArticlepeer-review

Abstract

The stability of Th<sup>4+</sup> to reduction in water is studied by DFT methods. The standard reduction potential (SRP) of homoleptic complexes including Th(H<sub>2</sub>O)<sub>9</sub><sup>4+</sup>, Th(H<sub>2</sub>O)<sub>10</sub><sup>4+</sup>, Th(NO<sub>3</sub>)<sub>4</sub>, Th(NO<sub>2</sub>)<sub>6</sub><sup>2–</sup>, Th(NO<sub>3</sub>)<sub>6</sub><sup>2–</sup>, Th(COT)<sub>2</sub>, Th(acac)<sub>4</sub>, ThCp<sub>4</sub>, ThF<sub>4</sub>, and ThCl<sub>4</sub> have been investigated. The values vary widely (from −3.50 V for Th(OH)<sub>4</sub> to −0.62 V for Th(NO<sub>3</sub>)<sub>4</sub> depending on whether the ligands are redox active (noninnocent) or not. Several additional topics of thorium chemistry are explored, including the hydrolysis mechanism of ThO<sub>2</sub>(H<sub>2</sub>O)<sub><i>n</i></sub>, <i>n</i> = 1, 2, 4, and the solution phase nonzero dipole moment of ThCp<sub>4</sub>. Dinuclear complexes are also characterized, including Th<sub>2</sub>O<sub>4</sub>, Th<sub>2</
Original languageEnglish
Pages (from-to)8169--8183
JournalThe Journal of Physical Chemistry: Part A
DOIs
StatePublished - 2016

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