A theoretical study into a trans-dioxo MnV porphyrin complex that does not follow the oxygen rebound mechanism in C-H bond activation reactions
A theoretical study into a trans-dioxo MnV porphyrin complex that does not follow the oxygen rebound mechanism in C-H bond activation reactions
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DOI：
10.1039/c5cc08734a
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发表时间：
2016-01-01
影响因子：
4.9
通讯作者：
Nam, Wonwoo
中科院分区：
文献类型：
--
作者：
Cho, Kyung-Bin;Nam, Wonwoo
已有的实验结果表明，反式二氧Mn-V卟啉配合物[（TF（4）TMAP）（OMnO）-O-V]（3+）的C-H键活化反应不是通过众所周知的氧反弹机制进行的，这在（FeO）-O-IV卟啉π-阳离子自由基反应中得到了很好的证明。在本研究中，理论计算提供了一个解释，通过参与C-H键活化反应，其中不能排除多自旋态的情况下的能量。
Previous experimental results revealed that the C-H bond activation reaction by a synthetic trans-dioxo Mn-V porphyrin complex, [(TF(4)TMAP)(OMnO)-O-V](3+), does not occur via the well-known oxygen rebound mechanism, which has been well demonstrated in (FeO)-O-IV porphyrin pi-cation radical reactions. In the present study, theoretical calculations offer an explanation through the energetics involved in the C-H bond activation reaction, where a multi-spin state scenario cannot be excluded.