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

Inorganic Chemistry
Daniel J GrantWilliam J Evans

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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Citations

Jun 7, 2012·Inorganic Chemistry·Juan DiwuThomas E Albrecht-Schmitt
Mar 16, 2016·Journal of the American Chemical Society·Ryan R LangeslayWilliam J Evans
Nov 27, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Yanqiu YangLinfeng Rao
Jan 26, 2018·Angewandte Chemie·Marta FalconeMarinella Mazzanti
Oct 23, 2015·Chemical Communications : Chem Comm·Justin K PaganoJaqueline L Kiplinger
Jun 24, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Erli Lu, Stephen T Liddle
Jul 5, 2019·Chemical Communications : Chem Comm·Guorui QinJianhua Cheng
Jun 4, 2014·Angewandte Chemie·Henry S La PierreKarsten Meyer
May 31, 2012·Journal of the American Chemical Society·Matthew J PolinskiThomas E Albrecht-Schmitt

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