Abstract
AbstractWe report the synthesis, characterization, and reactivity of [LFe3(PhPz)3OMn(sPhIO)][OTf]x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X‐ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X‐ray absorption spectroscopy provided unique insights into how changes in oxidation state (FeIII2FeIIMnII vs. FeIII3MnII) influence oxygen atom transfer in tetranuclear Fe3Mn clusters. In particular, a one‐electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.
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