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Organocopper(III) Spiro Complexes: Synthesis, Structural Characterization, and Redox Transformation
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2017-09-25 00:00:00 , DOI: 10.1021/jacs.7b08803
Liang Liu 1 , Miaomiao Zhu 1, 2 , Hai-Tao Yu 2 , Wen-Xiong Zhang 1 , Zhenfeng Xi 1, 3
Affiliation  

Reductive elimination of Cu(III) intermediates is often proposed as a key step in many copper-catalyzed or -mediated formation of C–C or C–heteroatom bonds. However, there still lacks concrete evidence on this key step, mainly because Cu(III) complexes are usually too unstable to be isolated and structurally characterized. In this work, novel organocopper(III) spiro complexes and their analogous organocopper(I) spiro complexes were synthesized and structurally characterized. Single-crystal X-ray structural analysis revealed that the spiro Cu(III) atom adopted a distorted square-planar geometry while its corresponding spiro Cu(I) atom was tetrahedrally coordinated. A redox transformation between these spiro Cu(I) and Cu(III) complexes was experimentally observed by reacting with reductants or oxidants, respectively. As concrete evidence, the organocopper(III) spiro compounds were found to form C–C bonds intramolecularly via reductive elimination.

中文翻译:

有机铜(III)螺络合物:合成,结构表征和氧化还原转化。

在许多铜催化或介导的C–C或C–杂原子键的形成中,通常建议采用还原消除Cu(III)中间体的关键步骤。但是,在这一关键步骤上仍然缺乏具体的证据,主要是因为Cu(III)配合物通常太不稳定而无法分离和结构表征。在这项工作中,新颖的有机铜(III)螺络合物及其类似的有机铜(I)螺络合物被合成并在结构上进行了表征。X射线单晶结构分析表明,螺Cu(III)原子采用扭曲的方平面几何形状,而其相应的螺Cu(I)原子为四面体配位。通过分别与还原剂或氧化剂反应,分别在实验中观察到了这些螺旋Cu(I)和Cu(III)配合物之间的氧化还原转化。作为具体证据,
更新日期:2017-09-26
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