Investigation of Uranium Tris(imido) Complexes: Synthesis, Characterization, and Reduction Chemistry of [U(NDIPP)3(thf)3]

被引：33

作者：

Anderson, Nickolas H. ^{[1
]}

Yin, Haolin ^{[2
]}

Kiernicki, John J. ^{[1
]}

Fanwick, Phillip E. ^{[1
]}

Schelter, Eric J. ^{[2
]}

Bart, Suzanne C. ^{[1
]}

机构：

[1] Purdue Univ, Dept Chem, HC Brown Lab, W Lafayette, IN 47907 USA

[2] Univ Penn, Dept Chem, P Roy & Diana T Vagelos Labs, Philadelphia, PA 19104 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 32期

关键词：

imido; magnetic properties; multiple bonds; reduction; uranium; IMIDO COMPLEXES; REACTIVITY; BIS(IMIDO); HYDROGENATION; ANALOGS;

D O I：

10.1002/anie.201503771

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Addition of KC8 to trivalent [UI3(thf)(4)] in the presence of three equivalents of 2,6-diisopropylphenylazide (N3DIPP) results in the formation of the hexavalent uranium tris(imido) complex [U(NDIPP)(3)(thf)(3)] (1) through a facile, single-step synthesis. The X-ray crystal structure shows an octahedral complex that adopts a facial orientation of the imido substituents. This structural trend is maintained during the single-electron reduction of 1 to form dimeric [U(NDIPP)(3){K(Et2O)}](2) (2). Variable-temperature/field magnetization studies of 2 show two independent U-V 5f(1) centers, with no antiferromagnetic coupling present. Characterization of these complexes was accomplished using single-crystal X-ray diffraction, variable-temperature (HNMR)-H-1 spectroscopy, as well as IR and UV/Vis absorption spectroscopic studies.

引用

页码：9386 / 9389

页数：4

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