Solvent, Anion, and Structural Effects on the Redox Potentials and UV−visible Spectral Properties of Mononuclear Manganese Corroles

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• 作者：Jing Shen ; Maya El Ojaimi ; Mohammed Chkounda ; Claude P. Gros ; Jean-Michel Barbe ; Jianguo Shao ; Roger Guilard ; Karl M. Kadish
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：September 1, 2008
• 年：2008
• 卷：47
• 期：17
• 页码：7717-7727
• 全文大小：355K
• 年卷期：v.47,no.17(September 1, 2008)
• ISSN：1520-510X

文摘

A series of manganese(III) corroles were investigated as to their electrochemistry and spectroelectrochemistry in nonaqueous solvents. Up to three oxidations and one reduction were obtained for each complex depending on the solvents. The main compound discussed in this paper is the meso-substituted manganese corrole, (Mes₂PhCor)Mn, and the main points are how changes in axially coordinated anion and solvent will affect the redox potentials and UV−vis spectra of each electrogenerated species in oxidation states of Mn(III), Mn(IV), or Mn(II). The anions OAc⁻, Cl⁻, CN⁻, and SCN⁻ were found to form five-coordinate complexes with the neutral Mn(III) corrole while two OH⁻ or F⁻ anions were shown to bind axially in a stepwise addition to give the five- and six-coordinate complexes in nonaqueous media. In each case, complexation with one or two anionic axial ligands led to an easier oxidation and a harder reduction as compared to the uncomplexed four-coordinate species.