Di- and Trinuclear Mixed-Valence Copper Amidinate Complexes from Reduction of Iodine
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- 作者：Andrew C. Lane ; Charles L. Barnes ; William E. Antholine ; Denan Wang ; Adam T. Fiedler ; Justin R. Walensky
- 刊名：Inorganic Chemistry
- 出版年：2015
- 出版时间：September 8, 2015
- 年：2015
- 卷：54
- 期：17
- 页码：8509-8517
- 全文大小：577K
- ISSN：1520-510X
文摘
Molecular examples of mixed-valence copper complexes through chemical oxidation are rare but invoked in the mechanism of substrate activation, especially oxygen, in copper-containing enzymes. To examine the cooperative chemistry between two metals in close proximity to each other we began studying the reactivity of a dinuclear Cu(I) amidinate complex. The reaction of [(2,6-Me2C6H3N)2C(H)]2Cu2, 1, with I2 in tetrahydrofuran (THF), CH3CN, and toluene affords three new mixed-valence copper complexes [(2,6-Me2C6H3N)2C(H)]2Cu2(渭2-I3)(THF)2, 2, [(2,6-Me2C6H3N)2C(H)]2Cu2(渭2-I) (NCMe)2, 3, and [(2,6-Me2C6H3N)2C(H)]3Cu3(渭3-I)2, 4, respectively. The first two compounds were characterized by UV鈥搗is and electron paramagnetic resonance spectroscopies, and their molecular structure was determined by X-ray crystallography. Both di- and trinuclear mixed-valence intermediates were characterized for the reaction of compound 1 to compound 4, and the molecular structure of 4 was determined by X-ray crystallography. The electronic structure of each of these complexes was also investigated using density functional theory.