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We report the synthesis of site-differentiated heterometallic clusters with three Fe centers and a single Mn site that binds water and hydroxide in multiple cluster oxidation states. Deprotonation of Fe III/II  3 Mn II -OH 2 clusters leads to internal reorganization resulting in formal oxidation at Mn to generate Fe III/II  3 Mn III -OH. 57 Fe Mössbauer spectroscopy reveals that oxidation state changes (three for Fe III/II  3 Mn-OH 2 and four for Fe III/II  3 Mn-OH clusters) occur exclusively at the Fe centers; the Mn center is formally Mn II when water is bound and Mn III when hydroxide is bound. Experimentally determined p K a (17.4) of the [Fe III  2 Fe II Mn II -OH 2 ] cluster and the reduction potentials of the [Fe 3 Mn-OH 2 ] and [Fe 3 Mn-OH] clusters were used to analyze the O-H bond dissociation enthalpies (BDE O-H ) for multiple cluster oxidation states. BDE O-H increases from 69 to 78 and 85 kcal/mol for the [Fe III Fe II  2 Mn II -OH 2 ], [Fe III  2 Fe II Mn II -OH 2 ], and [Fe III  3 Mn II -OH 2 ] clusters, respectively. Further insight of the proton and electron transfer thermodynamics of the [Fe 3 Mn-OH x ] system was obtained by constructing a potential-p K a diagram; the shift in reduction potentials of the [Fe 3 Mn-OH x ] clusters in the presence of different bases supports the BDE O-H values reported for the [Fe 3 Mn-OH 2 ] clusters. A lower limit of the p K a for the hydroxide ligand of the [Fe 3 Mn-OH] clusters was estimated for two oxidation states. These data suggest BDE O-H values for the [Fe III  2 Fe II Mn III -OH] and [Fe III  3 Mn III -OH] clusters are greater than 93 and 103 kcal/mol, which hints to the high reactivity expected of the resulting [Fe 3 Mn═O] in this and related multinuclear systems.

journal of the american chemical society

Thermodynamics of Proton and Electron Transfer in Tetranuclear Clusters with Mn–OH<sub>2</sub>/OH Motifs Relevant to H<sub>2</sub>O Activation by the Oxygen Evolving Complex in Photosystem II

Thermodynamics of Proton and Electron Transfer in Tetranuclear Clusters with Mn–OH2/OH Motifs Relevant to H2O Activation by the Oxygen Evolving Complex in Photosystem II

Thermodynamics of Proton and Electron Transfer in Tetranuclear Clusters with Mn–OH₂/OH Motifs Relevant to H₂O Activation by the Oxygen Evolving Complex in Photosystem II