Uranium and thorium hydride complexes as multielectron reductants: a combined neutron diffraction and quantum chemical study |
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Authors: | Grant Daniel J Stewart Timothy J Bau Robert Miller Kevin A Mason Sax A Gutmann Matthias McIntyre Garry J Gagliardi Laura Evans William J |
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Institution: | Department of Chemistry, University of Minnesota and Supercomputing Institute, Minneapolis, Minnesota 55455, USA. |
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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(5)Me(5))(2)UH(2)](2) (1) ? (C(5)Me(5))(2)UH](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(5)Me(5))(2)ThH](2), shows that the thorium(4+) to thorium(3+) hydride interconversion reaction is endothermic by 26 kcal/mol. |
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