| Literature DB >> 24304416 |
David E Herbert1, Davide Lionetti, Jonathan Rittle, Theodor Agapie.
Abstract
A series of tetranuclear oxo/hydroxo clusters comprised of three Fe centers and a redox-inactive metal (M) of various charge is reported. Crystallographic studies show an unprecedented Fe3M(μ4-O)(μ2-OH) core that remains intact upon changing M or the oxidation state of iron. Electrochemical studies reveal that the reduction potentials (E1/2) span a window of 500 mV and depend upon the Lewis acidity of M. Using the pKa of the M-aqua complex as a measure of Lewis acidity, these compounds display a linear dependence between E1/2 and acidity, with a slope of ∼70 mV per pKa unit. The current study of [Fe3MO(OH)] and previous ones of [Mn3MOn] (n = 2,4) moieties support the generality of the above relationship between the reduction potentials of heterometallic oxido clusters and the Lewis acidity of incorporated cations, as applied to clusters of different redox-active metals.Entities:
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Year: 2013 PMID： 24304416 PMCID： PMC3953215 DOI： 10.1021/ja4104974
Source DB: PubMed Journal: J Am Chem Soc ISSN： 0002-7863 Impact factor: 15.419