- 作者: 張志宏 ; 鄭淑華 ; 蘇玉龍
- 作者服務機構: 台灣大學化學系
- 中文摘要: A systematic study for the effect of axially coordinated monovalent anions on the electrode reactions of several manganese porphyrins in acetonitrile is presented. Potential shifts of the metal-centered reduction with changes in counterion were related to the degree of Mn(III)-counterion interaction. In the electrochemically induced ligand exchange, perchlorate anion replaces the other anions as axial ligand coordinated to Mn(III) at oxidation potential less than the first oxidation of manganese porphyrins. Formation constants for axial ligation of OH/sup -/ are calculated. One-electron oxidation of dihydroxide coordinated manganese porphyrins generate oxomanganese(IV) porphyrin complexes electrochemically. O= Mn/sup IV/ OEP(OH) is more thermodynamically stable than O= Mn/sup IV/TPP(OH), while O= Mn/sup IV/TpFPP(OH) cannot be generated electrochemically. In the presence of styrene or cyclohexene, the absorption spectra of oxomanganese(IV) porphyrins are changed to form manganese(III) porphyrins gradually, which indicates the oxygen atom transfer from oxomanganese(IV) porphyrins to the substrates.
- 英文摘要: --
- 中文關鍵字: Manganese Porphyrin; Redox Reaction; Axial Ligand; Alkene
- 英文關鍵字: 錳紫質;氧化還原反應;軸向配位基;烯類