Our recent results on determining the influence of first- and second-coordination sphere elements on the structures, spectroscopic properties, and reactivity of nonheme iron centers will be described. Nonheme iron centers are of interest because of their key roles in a wide range of metalloenzymes, as well as their potential for use in catalytic applications. Ligand design has been employed to include novel heteroatoms, such as sulfur, in the first-coordination sphere of iron-oxo and iron-peroxo species, which are key intermediates in nonheme Fe oxygenase chemistry. The discrimination of some of these species in giving intra- versus intermolecular sulfur oxidation will be discussed, including an iron(II)-thiolate complex that reacts with O2 to give an iron(II)-sulfinate complex, and a metastable Fe(IV)(O) complex that shows high selectivity for inter- versus intramolecular sulfoxidation. In the second-coordination sphere, substrate positioning leads to rapid arene hydroxylation, providing concrete evidence for a theoretical description regarding Fe(IV)(O) reactivity. The effects of proximal H-bond donors on Fe(IV)(O) and Fe(OOR) species will also be described.

Tuning of the first- and second-coordination spheres in nonheme iron complexes

247th National Meeting (2014)

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