关于锰（III）卟啉与次氯酸盐对烯烃环氧化反应机理的观察与评论
Observations and comments on the mechanism of epoxidation of alkenes by manganese(III) porphyrins with hypochlorite.
作者信息
Lee R W, Nakagaki P C, Balasubramanian P N, Bruice T C
机构信息
Department of Chemistry, University of California, Santa Barbara 93106.
出版信息
Proc Natl Acad Sci U S A. 1988 Feb;85(3):641-4. doi: 10.1073/pnas.85.3.641.
The kinetics of olefin epoxidation in a methylene chloride/water biphase containing a phase-transfer agent with hypochlorite as oxygen transfer reagent and manganese(III) tetraphenylporphyrin catalysts has been reinvestigated. The results do not support the accumulation of an intermediate composed of an alkene and a hypervalent metaloxo porphyrin. Second-order rate constants for oxygen transfer from hypochlorite to the manganese porphyrin, comproprotionation of the hypervalent manganese-oxo porphyrin with manganese(III) porphyrin, and olefin epoxidation by the hypervalent manganese-oxo porphyrin were obtained from experiments in a wet organic monophase.
以次氯酸盐作为氧转移试剂、四苯基卟啉锰为催化剂，在含有相转移剂的二氯甲烷/水双相体系中进行烯烃环氧化反应动力学的研究工作得以重新开展。研究结果并不支持由烯烃和高价金属氧代卟啉组成的中间体的积累。通过在湿有机单相中的实验，得出了次氯酸盐向锰卟啉转移氧、高价锰氧代卟啉与锰（III）卟啉的歧化反应以及高价锰氧代卟啉进行烯烃环氧化反应的二级速率常数。
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