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DOI: 10.1039/A607658K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1527-1532

Effect of ring size in macrocyclic dinuclear manganese(II) complexes upon their structure, properties and reactivity towards H2O2[hair space]

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Takanori Aono, Hisae Wada, Masami Yonemura, Masaaki Ohba, Hisashi Ōkawa and David E. Fenton

Abstract

A dinuclear manganese(II) complex [Mn2L4,4(O2CMe)2] has been prepared and its structure, properties and catalase-like function studied in comparison with the analogous [Mn2Lm,n(O2 CMe)2] [m,n = 2,3; 2,4; or 3,3; (Lm,n)2- denotes macrocycles containing two 2,6-bis(iminomethyl)-4-methylphenolate entities bridged through two lateral chains, (CH2)m and (CH2)n, at the imino nitrogens]. In the centrosymmetric [Mn2L4,4(O2CMe)2] a pair of manganese(II) ions are bridged by two phenolic oxygens of (L4,4)2- in the equatorial plane and by two acetate groups at the axial sites. The configuration about each Mn is pseudo-octahedral. The Mn · · · Mn separation is 2.978(1) Å. Cryomagnetic studies (4.2–300 K) indicated a significantly strong antiferromagnetic interaction (J = -5.0 cm-1 based on H = -2JS1S 2). The complex is oxidized at +0.35 V (vs. saturated calomel electrode) at a platinum electrode to a Mn2II,III complex. It catalyses the disproportionation of hydrogen peroxide in aqueous dimethylformamide. Based on ESR and visible spectroscopic studies, a catalytic mechanism involving the interconversion between MnIIMnIII(OH) and MnIIMnIV([double bond, length as m-dash]O) species is proposed.

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