"Oxidative Addition" of Halogens to Uranium(IV) Bis(amidophenolate) Complexes

被引：33

作者：

Matson, Ellen M. ^{[1
]}

Opperwall, Stacey R. ^{[1
]}

Fanwick, Phillip E. ^{[1
]}

Bart, Suzanne C. ^{[1
]}

机构：

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

来源：

INORGANIC CHEMISTRY | 2013年 / 52卷 / 12期

关键词：

REDUCTION CHEMISTRY; ELECTRON-TRANSFER; LIGAND; CONVENIENT; ARENE; CYCLOOCTATETRAENE; IMINOQUINONE; MOLECULE; THORIUM; HALIDE;

D O I：

10.1021/ic4009812

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A series of U(IV) complexes, ((R)ap)(2)U(THF)(2) [R = tert-butyl (t-Bu) (1), adamantyl (Ad) (2), diisopropylphenyl (dipp) (3)], supported by the redox-active 4,6-di-tert-butyl-2-(R)amidophenolate ligand, have been synthesized by salt metathesis of 2 equiv of the alkali metal salt of the ligand, M-2[(R)ap] [M = K (1 and 2), Na (3)], with UCl4. Exposure of these uranium complexes to 1 equiv of PhICl2 results in oxidative addition to uranium, forming the bis-(4,6-di-tert-butyl-2-(R)iminosemiquinone) ([(R)isq](1-)) uranium(IV) dichloride dimer, [((R)isq)(2)UCl](2)(mu(2)-Cl)(2) [R = t-Bu (4), Ad (5), dipp (6)]. The addition of iodine to 1 forms ((tBu)isq)(2)UI2(THF) (7), while the reactivity of I-2 with 2 and 3 results in decomposition. Complexes 1-7 have been characterized by H-1 NMR and electronic absorption spectroscopies. X-ray crystallography was employed to elucidate structural parameters of 2, 3, 5, and 7.

引用

页码：7295 / 7304

页数：10

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