含 Me6-tren 配体的 CuII-OOR（R = H 或枯基）配合物的光谱和计算特性研究。
Spectroscopic and computational characterization of CuII-OOR (R = H or cumyl) complexes bearing a Me6-tren ligand.
机构信息
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, Korea.
出版信息
Dalton Trans. 2011 Mar 14;40(10):2234-41. doi: 10.1039/c0dt01036g. Epub 2011 Jan 24.
Abstract
A copper(II)-hydroperoxo complex, Cu(Me(6)-tren)(OOH) (2), and a copper(ii)-cumylperoxo complex, Cu(Me(6)-tren)(OOC(CH(3))(2)Ph) (3), were synthesized by reacting Cu(Me(6)-tren)(CH(3)CN) (1) with H(2)O(2) and cumyl-OOH, respectively, in the presence of triethylamine. These intermediates, 2 and 3, were successfully characterized by various physicochemical methods such as UV-vis, ESI-MS, resonance Raman and EPR spectroscopies, leading us to propose structures of the Cu(II)-OOR species with a trigonal-bipyramidal geometry. Density functional theory (DFT) calculations provided geometric and electronic configurations of 2 and 3, showing trigonal bipyramidal copper(II)-OOR geometries. These copper(II)-hydroperoxo and -cumylperoxo complexes were inactive in electrophilic and nucleophilic oxidation reactions.
摘要
一种铜（II）-过氧配合物，[Cu(Me(6)-tren)(OOH)] + (2)，和一种铜（ii）-过氧化叔丁基配合物，[Cu(Me(6)-tren)(OOC(CH(3))(2)Ph)] + (3)，是通过将[Cu(Me(6)-tren)(CH(3)CN)] 2+ (1)与 H 2 O 2 和过氧化叔丁基在三乙胺的存在下反应分别合成的。这些中间体 2 和 3 通过各种物理化学方法如紫外可见光谱、ESI-MS、共振拉曼和 EPR 光谱成功地进行了表征，使我们提出了具有三角双锥几何形状的 Cu(II)-OOR 物种的结构。密度泛函理论 (DFT) 计算提供了 2 和 3 的几何和电子构型，显示出三角双锥铜（II）-OOR 几何形状。这些铜（II）-过氧配合物和过氧化叔丁基配合物在亲电和亲核氧化反应中是无活性的。
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