Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions

Nickolas H. Anderson, Jing Xie, Debmalya Ray, Matthias Zeller, Laura Gagliardi, Suzanne C. Bart

Research output: Contribution to journalArticle

29 Scopus citations

Abstract

Actinyl species, [AnO2]2+, are well-known derivatives of the f-block because of their natural occurrence and essential roles in the nuclear fuel cycle. Along with their nitrogen analogues, [An(NR)2]2+, actinyls are characterized by their two strong trans-An-element multiple bonds, a consequence of the inverse trans influence. We report that these robust bonds can be weakened significantly by increasing the number of multiple bonds to uranium, as demonstrated by a family of uranium(VI) dianions bearing four U-N multiple bonds, [M]2[U(NR)4] (M= Li, Na, K, Rb, Cs). Their geometry is dictated by cation coordination and sterics rather than by electronic factors. Multiple bond weakening by the addition of strong φ donors has the potential for applications in the processing of high-valent actinyls, commonly found in environmental pollutants and spent nuclear fuels.

Original languageEnglish (US)
Pages (from-to)850-855
Number of pages6
JournalNature Chemistry
Volume9
Issue number9
DOIs
StatePublished - Sep 1 2017

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