Synthesis of Asymmetrical Monobenzo-Substituted Cobalt Thioporphyrazines and Their Biomimetic Catalytic Property  

作　　者：Peng Zhou Juanjuan Jin Bingguang Zhang Changjun Yang Zehui Zhang Zhe Li Kejian Deng 

机构地区：[1]Key Laboratory of Catalysis and Material Sciences of the State Ethnic Affairs Commission & Ministry of Education, College of Chemistry and Material Sciences, South-Central University for Nationalities, Wuhan, Hubei 430074, China

出　　处：《Chinese Journal of Chemistry》2016年第10期1013-1020,共8页中国化学（英文版）

基　　金：This work was financially supported by National Natural Science Foundation of China （Nos. 20977115 and 21272281）, Natural Science Foundation of Hubei Province （No. 2014CFB919） and the S＆T Plan Innovation team of Wuhan city （No. 2015070504020220）.

摘　　要：Two novel monobenzo porphyrazines bearing nitro and methoxyl respectively on fused benzene ring were suc- cessfully synthesized. Also, an asymmetrical porphyrazine with one butylthio branch at the pyrrolic p-position sub- stituted by hydrogen atom was successfully isolated in the course of synthesis of symmetric octakis（butylthio） porphyrazine. Their corresponding cobalt complexes were subsequently obtained and characterized. Their catalytic ability was assessed by aerobic oxidation of benzoin, showing the highest benzil yield of 95.2% for 60 min. A pos- sible mechanism was also presented from the in-situ UV-Vis spectra, in which a novel and characteristic absorption peak of metal-oxo was observed. At the same time, similar results of the extended oxidation of benzyl alcohol also confirmed the reactive mechanism.Two novel monobenzo porphyrazines bearing nitro and methoxyl respectively on fused benzene ring were suc- cessfully synthesized. Also, an asymmetrical porphyrazine with one butylthio branch at the pyrrolic p-position sub- stituted by hydrogen atom was successfully isolated in the course of synthesis of symmetric octakis（butylthio） porphyrazine. Their corresponding cobalt complexes were subsequently obtained and characterized. Their catalytic ability was assessed by aerobic oxidation of benzoin, showing the highest benzil yield of 95.2% for 60 min. A pos- sible mechanism was also presented from the in-situ UV-Vis spectra, in which a novel and characteristic absorption peak of metal-oxo was observed. At the same time, similar results of the extended oxidation of benzyl alcohol also confirmed the reactive mechanism.

关 键 词：cobalt thioporphyrazines monobenzo-substituted derivatives aerobic oxidation of benzoin to benzil In-situ UV-Vis spectra mechanism of biomimetic catalysis 

分 类 号：O621.34[理学—有机化学] O614.812[理学—化学]