Covalency-Driven Dimerization of Plutonium(IV) in a Hydroxamate Complex

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• 作者：Mark A. Silver ; Samantha K. Cary ; Jared T. Stritzinger ; T. Gannon Parker ; Laurent Maron ; Thomas E. Albrecht-Schmitt
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：June 6, 2016
• 年：2016
• 卷：55
• 期：11
• 页码：5092-5094
• 全文大小：233K
• 年卷期：0
• ISSN：1520-510X

文摘

The reaction of formohydroxamic acid [NH(OH)CHO, FHA] with Pu^III should result in stabilization of the trivalent oxidation state. However, slow oxidation to Pu^IV occurs, which leads to formation of the dimeric plutonium(IV) formohydroxamate complex Pu₂(FHA)₈. In addition to being reductants, hydroxamates are also strong π-donor ligands. Here we show that formation of the Pu₂(FHA)₈ dimer occurs via covalency between the 5f orbitals on plutonium and the π* orbitals of FHA^– anions, which gives rise to a broad and intense ligand-to-metal charge-transfer feature. Time-dependent density functional theory calculations corroborate this assignment.