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A Pseudotetrahedral Uranium(V) Complex
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DOI：10.1021/acs.inorgchem.7b03139.png)
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摘要
En 中文
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 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.
Keyword:
X-RAY-ABSORPTION
ELECTRONIC-STRUCTURE
MAGNETIC-PROPERTIES
COORDINATION-COMPLEXES
ACTINIDE COMPLEXES
CRYSTAL-STRUCTURE
AMIDE COMPLEXES
METAL-COMPLEXES
BASIS-SETS
CHEMISTRY
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期刊
IF:
4.7
论文数:
4.9W
被引数:
10.5W
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