Reactivity difference in the oxidative nucleophilic reaction of peroxonickel(iii) intermediates with open-chain and macrocyclic systems
Reactivity difference in the oxidative nucleophilic reaction of peroxonickel(iii) intermediates with open-chain and macrocyclic systems
复制标题
开链和大环体系过氧镍(iii)中间体氧化亲核反应的反应活性差异
DOI：
10.1039/c9qi00465c
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发表时间：
2019
影响因子：
7
通讯作者：
Jaeheung Cho
中科院分区：
文献类型：
--
作者：
Seonggeun Yun;Nam Kwon;Seonghan Kim;Donghyun Jeong;Takehiro Ohta;Jaeheung Cho
合成了一种含Me 6-trien配体的过氧合镍（III）配合物，并通过UV-vis、共振拉曼、ESI-MS和EPR等物理方法对其结构进行了表征。密度泛函理论计算提供过氧镍（III）配合物的几何和电子构型。在氧化亲核反应（例如，醛脱氢酶）。通过比较开链和大环过氧镍（III）配合物在相同反应条件下的反应性，我们能够证明开链过氧镍（III）配合物在醛脱氨中的反应性比大环类似物高得多。这一结果提供了有趣的方面的反应性差异的开链与大环系统的金属配合物。
A peroxonickel(III) complex bearing the Me6-trien ligand, an open-chain analogue of the macrocyclic 12-TMC ligand, was synthesized and characterized by several physical methods, such as UV-vis, resonance Raman, ESI-MS and EPR. Density functional theory calculations provide geometric and electronic configurations of peroxonickel(III) complexes. The reactivity of the peroxonickel(III) intermediate was examined in oxidative nucleophilic reactions (e.g., aldehyde deformylation). By comparing the reactivities of the open-chain and macrocyclic peroxonickel(III) complexes under identical reaction conditions, we were able to demonstrate that the open-chain peroxonickel(III) complex is much more reactive than the macrocyclic analogue in aldehyde deformylation. This result provides intriguing aspects of the reactivity differences for open-chain vs. macrocyclic systems of metal complexes.