Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Redox Chemistry and Autoreduction of Non-$\mu$-oxo Dimer-Forming [5,10,15,20-Tetrakis(2,6-dichlorophenyl)porphyrinato] Manganese(III) Chloride by Hydroxide Ion

  • Published : 1996.10.20
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Abstract

The electrochemistry and the reaction of non-μ-oxo dimer-forming [5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato] manganese(Ⅲ) chloride [(Cl8TPP)MnⅢCl] with tetraethylammonium hydroxide in water [-OH(H2O)] have been investigated by electrochemical and spectroscopic methods under anaerobic conditions. The stronger autoreduction of (C18TPP)MnⅢCl by -OH(H2O) in comparison with (Me12TPP)MnⅢCl by -OH(CH3OH) in MeCN is explained as the influence of electronic effects on substituted phenyl groups bonded to meso-position of porphyrin ring and the positive shift of reduction potential (-0.11 V) for (C18TPP)MnⅢCl. The autoreduction of manganese(Ⅲ) porphyrin to manganese (Ⅱ) by this process is only observed when one axial position is occupied by a ligating solvent and OH- coordinates the other axial site. The results are discussed in relation to the mechanisms for the reduction of manganese(Ⅲ) porphyrin.

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