Binuclear metal complexes. XLII. Manganese(IV) complexes synthesized by oxidation of binuclear manganese(II) complexes of 2-(salicylideneamino)phenols with tetrachloro-o-benzoquinone.
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概要
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Manganese(IV) complexes Mn(R-R′-sap)<SUB>2</SUB>, where H<SUB>2</SUB>(R-R′-sap) denotes 2-(salicylideneamino)phenols with the substituent R on the salicylaldehyde ring and the R′ on the <I>o</I>-aminophenol ring, were prepared by the oxidation of binuclear manganese(II) complexes Mn<SUB>2</SUB>(R-R′-sap)<SUB>2</SUB> with tetrachloro-<I>o</I>-benzoquinone (TCOQ). The complexes showed magnetic moments corresponding to three unpaired electrons and strong absorptions in the region 15–20×10<SUP>3</SUP> cm<SUP>−1</SUP> attributable to CT transitions. Cyclic voltammograms of Mn(R-R′-sap)<SUB>2</SUB> showed two redox waves which can be interpreted in terms of a two-step reaction, Mn(IV)\rightleftharpoonsMn(III)\rightleftharpoonsMn(II). Both redox potentials of the first and the second processes depend on the substituents R and R′, and there is a good correlation between the redox potentials and Hammett's σ-values of R and R′ to the phenolic oxygen. Mn<SUB>2</SUB>(R-R′-sap)<SUB>2</SUB> reacts with TCOQ to give a binuclear manganese(III) complex Mn<SUB>2</SUB>(R-R′-sap)<SUB>2</SUB>(tcoq), which decomposes in the presence of water forming Mn(R-R′-sap)<SUB>2</SUB>.
- 公益社団法人 日本化学会の論文
著者
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Okawa Hisashi
Department Of Chemistry Faculty Of Science Kyushu University
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Nakamura Masaaki
Department Of Applied Physics Faculty Of Science Tokyo University Of Science
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Kida Sigeo
Department of Chemistry Wakayama University
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