Laser flash photolysis formation and direct kinetic studies of manganese(V)-oxo porphyrin intermediates
Laser flash photolysis formation and direct kinetic studies of manganese(V)-oxo porphyrin intermediates
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DOI：
10.1021/ja0377448
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发表时间：
2003-10-15
影响因子：
15
通讯作者：
Newcomb, M
中科院分区：
文献类型：
--
作者：
Zhang, R;Newcomb, M
在355 nm激光照射下，在乙腈中合成了高氯酸卟啉锰(Ⅲ)配合物，并对其进行了UV、−、Vis光谱和反应活性的表征。生成了四(五氟苯基)卟啉(2)、四苯基卟啉(4)和四(4-(N-甲基吡啶)基)卟啉(6)的MNV-oxo物种。2与底物反应的二级速率常数分别为： 6.1×105m-1s-1(顺式二苯乙烯)，1.3×105m-1s-1(二苯基甲烷)，1.3×105m-1s-1(乙苯)，0.55×105m-1s-1(乙苯-D10)。在顺式二苯乙烯和二苯基甲烷的氧化反应中，MNV-oxo物种的反应活性顺序为2>；6>；4。
Irradiation of porphyrin-manganese(III) perchlorate complexes in acetonitrile with 355 nm laser light gave MnV-oxo intermediates that were characterized by their UV−vis spectra and reactivities. The MnV-oxo species of tetrakis(pentafluorophenyl)porphyrin (2), tetraphenylporphyrin (4), and tetra-(4-(N-methylpyridiniumyl))porphyrin (6) were generated. Second-order rate constants for reactions of2with substrates were as follows: 6.1 × 105M-1s-1(cis-stilbene), 1.3 × 105M-1s-1(diphenylmethane), 1.3 × 105M-1s-1(ethylbenzene), and 0.55 × 105M-1s-1(ethylbenzene-d10). In oxidations ofcis-stilbene and diphenylmethane, the order of reactivity of the MnV-oxo species was2>6>4.