TY - JOUR
T1 - A Pseudotetrahedral Uranium(V) Complex
AU - Tondreau, Aaron M.
AU - Duignan, Thomas J.
AU - Stein, Benjamin W.
AU - Fleischauer, Valerie E.
AU - Autschbach, Jochen
AU - Batista, Enrique R.
AU - Boncella, James M.
AU - Ferrier, Maryline G.
AU - Kozimor, Stosh A.
AU - Mocko, Veronika
AU - Neidig, Michael L.
AU - Cary, Samantha K.
AU - Yang, Ping
N1 - Publisher Copyright:
Copyright © 2018 American Chemical Society.
PY - 2018/7/16
Y1 - 2018/7/16
N2 - 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 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.
AB - 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 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.
UR - https://www.scopus.com/pages/publications/85050001652
U2 - 10.1021/acs.inorgchem.7b03139
DO - 10.1021/acs.inorgchem.7b03139
M3 - Article
C2 - 29975519
AN - SCOPUS:85050001652
SN - 0020-1669
VL - 57
SP - 8106
EP - 8115
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 14
ER -