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

Abstract

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 π donors has the potential for applications in the processing of high-valent actinyls, commonly found in environmental pollutants and spent nuclear fuels.

Authors:
 [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
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1489152
DOE Contract Number:  
SC0008479; SC0002183; AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 9; Journal Issue: 9; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English

Citation Formats

Anderson, Nickolas H., Xie, Jing, Ray, Debmalya, Zeller, Matthias, Gagliardi, Laura, and Bart, Suzanne C. Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions. United States: N. p., 2017. Web. doi:10.1038/NCHEM.2767.
Anderson, Nickolas H., Xie, Jing, Ray, Debmalya, Zeller, Matthias, Gagliardi, Laura, & Bart, Suzanne C. Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions. United States. doi:10.1038/NCHEM.2767.
Anderson, Nickolas H., Xie, Jing, Ray, Debmalya, Zeller, Matthias, Gagliardi, Laura, and Bart, Suzanne C. Mon . "Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions". United States. doi:10.1038/NCHEM.2767.
@article{osti_1489152,
title = {Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions},
author = {Anderson, Nickolas H. and Xie, Jing and Ray, Debmalya and Zeller, Matthias and Gagliardi, Laura and Bart, Suzanne C.},
abstractNote = {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.},
doi = {10.1038/NCHEM.2767},
journal = {Nature Chemistry},
issn = {1755-4330},
number = 9,
volume = 9,
place = {United States},
year = {2017},
month = {4}
}

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