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Title: 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.
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:
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