12-05

Mononuclear and dinuclear manganese compounds stabilized by supramolecular interactions, Dalton Trans. 41 (2012) 10249-10257

M. Viciano-Chumillas, M. Giménez-Marqués, S. Tanase, I. Mutikainen, U. Turpeinen, J.M.M. Smits, R. de Gelder, L.J. de Jongh and J. Reedijk

Abstract: New manganese compounds [Mn(HphpzMe)(2)(H(2)phpzMe)(HCO(2))] (1), Mn(2)(phpzMe)(2)(HphpzMe)(2)(OCH(3))]·2CH(3)OH (2), Na{[Mn(HphpzPh)(phpzPh)(MeOH)(2)](2)}(HCO(2)) (3), [Mn(HphpzPh)(2)(EtOH)(2)]ClO(4)·2EtOH (4) and [Mn(HphpzPh)(2)N(3)] (5) were synthesized and characterized with various techniques. 1, 4 and 5 are mononuclear manganese(III) compounds, 2 is a mixed-valence dinuclear manganese(III/IV) compound, and 3 is a trinuclear compound containing two manganese(III) ions and a sodium(I) ion. A remarkable feature is the spontaneous formation of the formate ion as a result of the methanol or methoxide oxidation in compounds 1 and 3. Using ethanol precludes the formation of the formate and compound 4 is obtained. The molecular structure of all compounds is stabilized by supramolecular interactions, including strong hydrogen bonding and π-π interactions.