A Pseudotetrahedral Uranium(V) Complex
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(NCySiMe 3) x(Cl) 4–x, where x = 2, 3, or 4. The diamide was then isolated as a bimetallic, bridging lithium chloride adduct ((UCl 2(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 U V 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 U IV and U V tetraamide complexes. Spectroscopic investigations consisting of UV–vis, NIR, MCD, EPR, and U L 3-edge XANES, along with density functional and wave function calculations, of the four-coordinate U IV and U V complexes have been used to understand the electronic structure of these pseudotetrahedral complexes.
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- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. at Buffalo, NY (United States). Dept. of Chemistry
- Univ. of Rochester, NY (United States). Dept. of Chemistry
- Univ. at Buffalo, NY (United States). Dept. of Chemistry
- Publication Date:
- Report Number(s):
- LA-UR-18-21979
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- AC52-06NA25396; SC0016002; SC0001136; AC02-76SF00515
- 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)
- Research Org:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); SLAC National Accelerator Lab., Menlo Park, CA (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)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
- OSTI Identifier:
- 1460655
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.,
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. 2018.
"A Pseudotetrahedral Uranium(V) Complex". United States.
doi:10.1021/acs.inorgchem.7b03139.
@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}
}