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

Journal Article · · Nature Chemistry
DOI:https://doi.org/10.1038/NCHEM.2767· OSTI ID:1489152
 [1];  [2];  [2];  [3];  [2];  [1]
  1. Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
  3. Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry; Youngstown State Univ., OH (United States). Dept. of Chemistry
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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 π donors has the potential for applications in the processing of high-valent actinyls, commonly found in environmental pollutants and spent nuclear fuels.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Office of Science (SC)
DOE Contract Number:
SC0008479; SC0002183; AC02-05CH11231
OSTI ID:
1489152
Journal Information:
Nature Chemistry, Vol. 9, Issue 9; ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English

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