School of Chemistry, College Green, Trinity College Dublin, The University of Dublin, Dublin 2 D02 PN40, Ireland.
National Synchrotron Light Source II, Brookhaven National Laboratory, Case Western Reserve University Center for Synchrotron Biosciences, Upton, New York 11973, United States.
Inorg Chem. 2020 Oct 5;59(19):13952-13961. doi: 10.1021/acs.inorgchem.0c01618. Epub 2020 Sep 21.
Metal-halides that perform proton coupled electron-transfer (PCET) oxidation are an important new class of high-valent oxidant. In investigating metal-dihalides, we reacted [Fe(Cl)(T(OMe)PP)] (, T(OMe)PP = -tetra(4-methoxyphenyl)porphyrinyl) with (dichloroiodo)benzene. An Fe--chloro-isoporphyrin complex [Fe(Cl)(T(OMe)PP-Cl)] () was obtained. was characterized by electronic absorption, H NMR, EPR, and X-ray absorption spectroscopies and mass spectrometry with support from computational analyses. was reacted with a series of hydrocarbon substrates. The measured kinetic data exhibited a nonlinear behavior, whereby the oxidation followed a hydrogen-atom-transfer (HAT) PCET mechanism. The -chlorine atom was identified as the HAT agent. In one case, a halogenated product was identified by mass spectrometry. Our findings demonstrate that oxo-free hydrocarbon oxidation with heme systems is possible and show the potential for iron-dihalides in oxidative hydrocarbon halogenation.
进行质子偶联电子转移 (PCET) 氧化的金属卤化物是一类重要的新型高价氧化剂。在研究金属二卤化物时，我们将 [Fe(Cl)(T(OMe)PP)]（，T(OMe)PP = -四(4-甲氧基苯基)卟啉基）与（二氯碘苯）反应。得到了一个 Fe--氯异卟啉配合物 [Fe(Cl)(T(OMe)PP-Cl)]（）。通过电子吸收、H NMR、EPR 和 X 射线吸收光谱以及计算分析得到了支持。与一系列烃基底物反应。测量的动力学数据表现出非线性行为，其中氧化遵循氢原子转移 (HAT) PCET 机制。-氯原子被确定为 HAT 试剂。在一种情况下，通过质谱鉴定出卤化产物。我们的发现表明，无氧化的血红素体系可以实现烃类的氧化，并且展示了铁二卤化物在氧化烃卤化中的潜力。
