Identification of the+2 Oxidation State for Uranium in a Crystalline Molecular Complex, [K(2.2.2-Cryptand)][(C5H4SiMe3)3U]

被引：205

作者：

MacDonald, Matthew R. ^{[1
]}

Fieser, Megan E. ^{[1
]}

Bates, Jefferson E. ^{[1
]}

Ziller, Joseph W. ^{[1
]}

Furche, Filipp ^{[1
]}

Evans, William J. ^{[1
]}

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 36期

基金：

美国国家科学基金会;

关键词：

TRIS(ETA-5-CYCLOPENTADIENYL) ACTINIDE COMPLEXES; CHEMISTRY; REDUCTION; REACTIVITY; LIGANDS;

D O I：

10.1021/ja406791t

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Flash reduction of Cp'U-3 (Cp' = C5H4SiMe3) in a column of potassium graphite in the presence of 2.2.2-cryptand generates crystalline [K(2.2.2-cryptand)][Cp'U-3], the first isolable molecular U2+ complex. To ensure that this was not the U3+ hydride, [K(2.2.2-cryptand)][Cp'3UH], which could be crystallo-graphically similar, the hydride complex was synthesized by addition of KH to Cp'U-3 and by reduction of H-2 by the U2+ complex and was confirmed to be a different compound. Density functional theory calculations indicate a 5f(3)6d(1) quintet ground state for the [Cp'U-3](-) anion and match the observed strong transitions in its optical spectrum.

引用

页码：13310 / 13313

页数：4

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