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Title: A Pseudotetrahedral Uranium(V) Complex

Abstract

A series of uranium amides were synthesized from N,N,N-cyclohexyl(trimethylsilyl)lithium amide [Li][N(TMS)Cy] and uranium tetrachloride to give U(NCySiMe3)x(Cl)4–x, where x = 2, 3, or 4. The diamide was then isolated as a bimetallic, bridging lithium chloride adduct ((UCl2(NCyTMS)2)2-LiCl(THF)2), and the tris(amide) was isolated as the lithium chloride adduct of the monometallic species (UCl(NCyTMS)3-LiCl(THF)2). The tetraamide complex was isolated as the four-coordinate pseudotetrahedron. Cyclic voltammetry revealed an easily accessible reversible oxidation wave, and upon chemical oxidation, the UV amido cation was isolated in near-quantitative yields. The synthesis of this family of compounds allows a direct comparison of the electronic structure and properties of isostructural UIV and UV tetraamide complexes. Spectroscopic investigations consisting of UV–vis, NIR, MCD, EPR, and U L3-edge XANES, along with density functional and wave function calculations, of the four-coordinate UIV and UV complexes have been used to understand the electronic structure of these pseudotetrahedral complexes.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [3]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. at Buffalo, NY (United States). Dept. of Chemistry
  3. Univ. of Rochester, NY (United States). Dept. of Chemistry
  4. Univ. at Buffalo, NY (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1460655
Report Number(s):
LA-UR-18-21979
Journal ID: ISSN 0020-1669; TRN: US1901890
Grant/Contract Number:  
AC52-06NA25396; SC0016002; SC0001136; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 14; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY

Citation Formats

Tondreau, Aaron M., Duignan, Thomas J., Stein, Benjamin W., Fleischauer, Valerie E., Autschbach, Jochen, Batista, Enrique R., Boncella, James M., Ferrier, Maryline G., Kozimor, Stosh A., Mocko, Veronika, Neidig, Michael L., Cary, Samantha K., and Yang, Ping. A Pseudotetrahedral Uranium(V) Complex. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.7b03139.
Tondreau, Aaron M., Duignan, Thomas J., Stein, Benjamin W., Fleischauer, Valerie E., Autschbach, Jochen, Batista, Enrique R., Boncella, James M., Ferrier, Maryline G., Kozimor, Stosh A., Mocko, Veronika, Neidig, Michael L., Cary, Samantha K., & Yang, Ping. A Pseudotetrahedral Uranium(V) Complex. United States. doi:10.1021/acs.inorgchem.7b03139.
Tondreau, Aaron M., Duignan, Thomas J., Stein, Benjamin W., Fleischauer, Valerie E., Autschbach, Jochen, Batista, Enrique R., Boncella, James M., Ferrier, Maryline G., Kozimor, Stosh A., Mocko, Veronika, Neidig, Michael L., Cary, Samantha K., and Yang, Ping. Thu . "A Pseudotetrahedral Uranium(V) Complex". United States. doi:10.1021/acs.inorgchem.7b03139. https://www.osti.gov/servlets/purl/1460655.
@article{osti_1460655,
title = {A Pseudotetrahedral Uranium(V) Complex},
author = {Tondreau, Aaron M. and Duignan, Thomas J. and Stein, Benjamin W. and Fleischauer, Valerie E. and Autschbach, Jochen and Batista, Enrique R. and Boncella, James M. and Ferrier, Maryline G. and Kozimor, Stosh A. and Mocko, Veronika and Neidig, Michael L. and Cary, Samantha K. and Yang, Ping},
abstractNote = {A series of uranium amides were synthesized from N,N,N-cyclohexyl(trimethylsilyl)lithium amide [Li][N(TMS)Cy] and uranium tetrachloride to give U(NCySiMe3)x(Cl)4–x, where x = 2, 3, or 4. The diamide was then isolated as a bimetallic, bridging lithium chloride adduct ((UCl2(NCyTMS)2)2-LiCl(THF)2), and the tris(amide) was isolated as the lithium chloride adduct of the monometallic species (UCl(NCyTMS)3-LiCl(THF)2). The tetraamide complex was isolated as the four-coordinate pseudotetrahedron. Cyclic voltammetry revealed an easily accessible reversible oxidation wave, and upon chemical oxidation, the UV amido cation was isolated in near-quantitative yields. The synthesis of this family of compounds allows a direct comparison of the electronic structure and properties of isostructural UIV and UV tetraamide complexes. Spectroscopic investigations consisting of UV–vis, NIR, MCD, EPR, and U L3-edge XANES, along with density functional and wave function calculations, of the four-coordinate UIV and UV complexes have been used to understand the electronic structure of these pseudotetrahedral complexes.},
doi = {10.1021/acs.inorgchem.7b03139},
journal = {Inorganic Chemistry},
number = 14,
volume = 57,
place = {United States},
year = {2018},
month = {7}
}

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