期刊
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
卷 24, 期 1-3, 页码 90-97出版社
WORLD SCI PUBL CO INC
DOI: 10.1142/S1088424619500780
关键词
cobalt complex; porphycene; ligand reduction; dehalogenation reaction
资金
- JSPS KAKENHI [18H04265, JP16H04119, JP17H04875]
- JSPS [AJ179063(29-9111-t11)]
- PAN [AJ179063(29-9111-t11)]
- Toyota Physical and Chemical Research Institute
- Tonen General Sekiyu
- Casio Science Promotion Foundation
- Kyushu University QR program
- Grants-in-Aid for Scientific Research [18H04265] Funding Source: KAKEN
The cobalt complexes of meso-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 the meso-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 the meso-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, i.e. the cobalt porphycenes.
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