Electrochemical properties and catalytic reactivity of cobalt complexes with redox-active meso-substituted porphycene ligands
Electrochemical properties and catalytic reactivity of cobalt complexes with redox-active meso-substituted porphycene ligands
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具有氧化还原活性内消旋取代卟啉配体的钴配合物的电化学性质和催化反应活性
DOI：
10.1142/s1088424619500780
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发表时间：
2020
影响因子：
1.5
通讯作者：
Hisaeda Yoshio
中科院分区：
文献类型：
--
作者：
Koide Taro;Zhou Zihan;Xu Ning;Yano Yoshio;Ono Toshikazu;Luo Zhongli;Shimakoshi Hisashi;Hisaeda Yoshio
合成并表征了meso-芳基取代卟啉钴配合物。配合物的还原电位随着取代基吸电子能力的增强而向正方向移动，但配合物的吸收光谱等光学性质相似.这表明，配合物的分子轨道的能级被改变的介位取代基，而轨道的间隙没有显着改变。配合物的单电子还原没有提供Co（I）物种，但配体还原的自由基阴离子，其特征在于通过电化学。所产生的配体还原的物种与烷基卤化物反应，形成Co（III）-烷基络合物。结果表明，电解反应的还原电位可直接由卟啉的取代基控制。同时还研究了三氯甲苯的催化反应，发现催化剂的还原电位改变了反应产物的比例。钴卟啉
The cobalt complexes ofmeso-aryl substituted porphycenes were synthesized and characterized. The reduction potentials of the complexes were shifted to the positive side depending on the strength of the electron-withdrawing properties of themeso-substituents, while the optical properties, such as the absorption spectra of these complexes, were similar. This suggests that the energy levels of the molecular orbitals of the complexes were changed by themeso-substituents while the gaps of the orbitals were not significantly changed. The one-electron reduction of the complex did not afford the Co(I) species, but the ligand-reduced radical anion, which was characterized by electrospectrochemistry. The generated ligand-reduced species reacted with alkyl halides to form the Co(III)-alkyl complex. As a result, the reduction potential of the electrolytic reaction could be directly controlled by the substituents of the porphycene. The catalytic reaction with trichloromethylbenzene was also performed and it was found that the ratio of the obtained products was changed by the reduction potentials of the catalyst,. the cobalt porphycenes.
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