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

作者：Anderson Nickolas H; Xie Jing; Ray Debmalya; Zeller Matthias; Gagliardi Laura; Bart Suzanne C^*

来源：Nature Chemistry, 2017, 9(9): 850-855.

DOI：10.1038/NCHEM.2767

Actinyl species, [AnO(2)](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 pi donors has the potential for applications in the processing of high-valent actinyls, commonly found in environmental pollutants and spent nuclear fuels.

• 出版日期2017-9