Uranium and Thorium Hydride Complexes as Multielectron Reductants: A Combined Neutron Diffraction and Quantum Chemical Study

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• 作者：Daniel J. Grant ; Timothy J. Stewart ; Robert Bau ; Kevin A. Miller ; Sax A. Mason ; Matthias Gutmann ; Garry J. McIntyre ; Laura Gagliardi ; William J. Evans
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：March 19, 2012
• 年：2012
• 卷：51
• 期：6
• 页码：3613-3624
• 全文大小：597K
• 年卷期：v.51,no.6(March 19, 2012)
• ISSN：1520-510X

文摘

The unusual uranium reaction system in which uranium(4+) and uranium(3+) hydrides interconvert by formal bimetallic reductive elimination and oxidative addition reactions, [(C₅Me₅)₂UH₂]₂ (1) [(C₅Me₅)₂UH]₂ (2) + H₂, was studied by employing multiconfigurational quantum chemical and density functional theory methods. 1 can act as a formal four-electron reductant, releasing H₂ gas as the byproduct of four H₂/H^{鈥?/sup> 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 H₂ pressure as part of this study. The interconversion of the uranium(4+) and uranium(3+) hydride species was calculated to be near thermoneutral (鈭? kcal/mol). Comparison with the unknown thorium analogue, [(C₅Me₅)₂ThH]₂, shows that the thorium(4+) to thorium(3+) hydride interconversion reaction is endothermic by 26 kcal/mol.}