Uranium and thorium hydride complexes as multielectron reductants: A combined neutron diffraction and quantum chemical study

Daniel J. Grant, Timothy J. Stewart, Robert Bau, Kevin A. Miller, Sax A. Mason, Matthias Gutmann, Garry J. McIntyre, Laura Gagliardi, William J. Evans

Research output: Contribution to journalArticlepeer-review

25 Scopus citations

Abstract

The unusual uranium reaction system in which uranium(4+) and uranium(3+) hydrides interconvert by formal bimetallic reductive elimination and oxidative addition reactions, [(C 5Me 5) 2UH 2] 2 (1) ⇌ [(C 5Me 5) 2UH] 2 (2) + H 2, was studied by employing multiconfigurational quantum chemical and density functional theory methods. 1 can act as a formal four-electron reductant, releasing H 2 gas as the byproduct of four H 2/H - redox couples. The calculated structures for both reactants and products are in good agreement with the X-ray diffraction data on 2 and 1 and the neutron diffraction data on 1 obtained under H 2 pressure as part of this study. The interconversion of the uranium(4+) and uranium(3+) hydride species was calculated to be near thermoneutral (∼-2 kcal/mol). Comparison with the unknown thorium analogue, [(C 5Me 5) 2ThH] 2, shows that the thorium(4+) to thorium(3+) hydride interconversion reaction is endothermic by 26 kcal/mol.

Original languageEnglish (US)
Pages (from-to)3613-3624
Number of pages12
JournalInorganic chemistry
Volume51
Issue number6
DOIs
StatePublished - Mar 19 2012

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