Determination of Basicity of Core X and Terminal Y Ligands (X, Y = S and Se) of Reduced, Oxidized, and Super-Oxidized Forms of [Fe4X4(YAd)4]2− (Ad = 1-Adamantyl) in Aqueous Solutions

A series of [Fe4X4(YAd)4]2− (X, Y = S, Se; Ad = 1-adamantyl) were prepared as a model of high potential iron–sulfur proteins. Hydrolysis of the clusters was effectively depressed in aqueous poly[2-(dimethylamino)hexanamide] (PDAH) solutions due to the enbedding effect in hydrophobic environment and/or inhibition of dissociation of the terminal ligand into the aqueous media. Cyclic voltammetry of those clusters in aqueous PDAH solutions showed pH-dependent redox potentials of not only the [Fe4X4]+/2+ but also the [Fe4X4]2+/3+ (X = S and Se) couples, resulting from redox-linked protonation reactions of three oxidation states of [Fe4X4(YAd)4]n− (n = 1—3). pKavalues of the reduced, oxidized, and super-oxidized forms of [Fe4X4(YAd)4]2− were determined by computer simulation of the pH dependent redox potentials. The basicity of the core X (X = S and Se) of three oxidation states of [Fe4X4(YAd)4]n− (n = 1, 2, 3) was stronger than the terminal YAd (Y = S and Se) ligands: in the case of the mono-protonated [Fe4X4(...

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