A Novel Carboxylate-Free Ferromagnetic Trinuclear μ3-Oxo−Manganese(III) Complex with Distorted Pentagonal-Bipyramidal Metal Centers

In methanol, the reaction of Mn(ClO(4))(2).6H(2)O and 1,2-bis(biacetylmonoximeimino)ethane (H(2)bamen) in the presence of triethylamine affords a trinuclear complex having the formula [Mn(3)(mu(3)-O)(mu(3)-bamen)(3)]ClO(4).2H(2)O. The structure of this complex shows a symmetric planar central [Mn(III)(3)(mu(3)-O)] unit coordinated to three hexadentate bridging (via oximate groups) ligands. The N(4)O(3) coordination sphere around each metal center is very close to pentagonal-bipyramidal. A cyclic voltammogram of the complex displays two reversible and an irreversible response due to Mn(III)(3) --> Mn(III)(2)Mn(IV), Mn(III)(2)Mn(IV) --> Mn(III)Mn(IV)(2), and Mn(III)Mn(IV)(2) --> Mn(IV)(3) oxidation processes, respectively. Cryomagnetic data reveal that the complex is ferromagnetic.