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