Until very recently the Ni and Cu corroles, already described in the sixties, were regarded as the MII complexes 1 (M = Ni, Cu). Some doubt arose about this interpretation after the existence of FeIV corroles demonstrated that corroles can stabilize metals in unusual oxidation states. Thorough physical studies have now shown that the metal atoms in the Ni and Cu corroles do in fact have the formal oxidation state +III (2).
We report here experimental evidence for the formation in the solid state of a new binuclear Fe (III) 2(mu-OMe) 2(HL) 4 complex (H 2L is 2-salicyloylhydrazono-1,3-dithiolane). The isostructural Mn (III) 2(mu-OMe) 2(HL) 4 complex has provided the strongest ferromagnetic interaction value (J approximately 20 cm (-1)) between Mn (III) ions to date. The new iron binuclear compound presented in this study shows antiferromagnetic intramolecular coupling, which agrees with the theoretical study that we previously proposed. During our synthetic work, we also observed an unexpected spontaneous reduction of the new Fe (III)(HL) 2Cl,S complex to the new Fe (II)(H 2L) 2Cl 2 high-spin mononuclear complex. This process has been checked by cyclo-voltammetry as well as pseudosteady voltammetry.
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