四乙氧基羰基卟啉铁(Ⅲ)配合物对苯乙烯的催化氧化  

Catalytic Styrene Oxidation Properties by Iron Ⅲ Tetrakis-(Ethoxycarbonyl)Porphyrin

作　　者：杨铭[1] 汪华华[2] 刘海洋[2] YANG Ming;WANG Huahua;LIU Haiyang(School of Chemical Engineering and Technology,Guangdong Industry Polytechnic,Guangzhou 510300,China;Department of Chemistry,South China University of Technology,Guangzhou 510641,China)

机构地区：[1]广东轻工职业技术学院轻化工技术学院,广东广州510300 [2]华南理工大学化学系,广东广州510641

出　　处：《广东轻工职业技术学院学报》2022年第3期9-14,共6页Journal of Guangdong Industry Polytechnic

基　　金：国家自然科学基金(21371059);广东轻工职业技术学院科研启动基金资助课题(KJ2020-013)。

摘　　要：卟啉铁配合物作为催化剂,在众多的有机反应中均有潜在的应用。合成一种新的中位取代的卟啉配合物,5,10,15,20-四乙氧基羰基卟啉铁配合物(Fe^(Ⅲ)TECPCl),并进行循环伏安、质谱、紫外、XPS等表征。以Fe^(Ⅲ)TECPCl为催化剂对苯乙烯进行催化氧化的研究,发现TBHP为氧源时产率最高,主要产物为苯甲醛,过程涉及氧气参与中间体自由基的生成,发现轴向配体咪唑可促进自由基的生成。Fe^(Ⅲ)TECPCl以PhIO或m-CPBA作为氧源主要产物是环氧苯乙烷和苯乙醛,可能涉及到高价态的Fe(V)-oxo卟啉或者由Fe(V)-oxo卟啉歧化生成Fe(Ⅵ)-oxo卟啉中间体。Porphyrin iron complexes as catalysts have potential applications in many organic reactions.In this study,a new meso substituted porphyrin complex,5,10,15,20-tetrakis(ethoxycarbonyl)porphyrinatoiron(Fe^(Ⅲ)TECPCL)was synthesized and characterized by cyclic voltammetry,mass spectrometry,UV-Vis and XPS.The catalytic oxidation of styrene with Fe^(Ⅲ)TECPC as catalyst was studied.It was found that the highest yield was obtained when TBHP was the oxygen source,and the main product was benzaldehyde.The process involved oxygen participating in the formation of intermediate free radicals.It was found that the axial ligand imidazole could promote the formation of free radicals.The main products of Fe^(Ⅲ)TECPCL using PhIO or m-CPBA as oxygen source are phenylene acetaldehyde and styrene epoxide,which may involve high valence Fe(Ⅴ)-oxo porphyrin or Fe(Ⅴ)-oxo porphyrin disproportionation to form Fe(Ⅵ)-oxo porphyrin intermediates.

关 键 词：卟啉 铁 催化氧化 苯乙烯 

分 类 号：O641.4[理学—物理化学]