Valence Tautomerism in a High-Valent Manganese-Oxo Porphyrinoid Complex Induced by a Lewis Acid
Valence Tautomerism in a High-Valent Manganese-Oxo Porphyrinoid Complex Induced by a Lewis Acid
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DOI：
10.1021/ja304609n
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发表时间：
2012-06-27
影响因子：
15
通讯作者：
Goldberg, David P.
中科院分区：
文献类型：
--
作者：
Leeladee, Pannee;Baglia, Regina A.;Goldberg, David P.
刘易斯酸Zn ~（2+）与（TBP（8）Cz）Mn-V（O）的加成反应导致价态互变异构，形成[（TBP（8）Cz（+中心点））Mn-IV（O）-Zn ~（2+）]。通过UV-vis、EPR、Evans方法和H-1 NMR对该新物种进行了表征，并得到了DFT计算的支持。除去Zn 2+定量地恢复了起始材料。Zn ~（2+）的存在强烈影响电子转移和氢原子转移反应。
Addition of the Lewis acid Zn2+ to (TBP(8)Cz)Mn-V(O) induces valence tautomerization, resulting in the formation of [(TBP(8)Cz(+center dot))Mn-IV(O)-Zn2+]. This new species was characterized by UV-vis, EPR, the Evans method, and H-1 NMR and supported by DFT calculations. Removal of Zn2+ quantitatively restores the starting material. Electron-transfer and hydrogen-atom-transfer reactions are strongly influenced by the presence of Zn2+.