Heterometallic effects in metal-oxide clusters are of interest because of their relevance to both natural systems (heterometallic enzymatic active sites such as Photosystem II) and artificial materials (mixed-metal oxide catalysts for energy conversion reactions such as dioxygen reduction and water oxidation). In particular, the influence of Lewis acidic, redox-inactive metal centers on redox processes in many such systems is not fully understood. To gain insight into how redox-active metal clusters are modulated by redox-inactive metal centers, a series of tetranuclear oxo/hydroxo clusters were prepared comprised of three Fe centers and a redox-inactive metal (M). These clusters were found to contain a Fe3M(�4-O)(�2-OH) core (M = Ca, Sr, Zn, La, Sc), and were characterized by single-crystal X-ray diffraction, M�ssbauer spectroscopy, and cyclic voltammetry. The effects of the redox-inactive metal centers on the properties and reactivity of these tetranuclear clusters will be discussed.

Heterometallic effects in tetrametallic triiron clusters

248th National Meeting (2014)

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