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Tuning the Fe(II/III) Redox Potential in Nonheme Fe(II)-Hydroxo Complexes through Primary and Secondary Coordination
Zachary Gordon1, Michael J Drummond1, Ellen M Matson1
1Department of Chemistry, University of Illinois at Urbana-Champaign , 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
Abstract:
The derivatization of the imino-functionalized tris(pyrrolylmethyl)amine ligand framework, N(XpiR)3 (XLR; X = H, Br; R = cyclohexyl (Cy), phenyl (Ph), 2,6- diisopropylphenyl (DIPP)), is reported. Modular ligand synthesis allows for facile modification of both the primary and secondary coordination sphere electronics. The iron(II)-hydroxo complexes, N(XpiR)(XafaR)2Fe(II)OH (XLRFeIIOH), are synthesized to establish the impact of the ligand modifications on the complexes' electronic properties, including their chemical and electrochemical oxidation. Cyclic voltammetry demonstrates that the Fe(II/III) redox couple spans a 400 mV range across the series. The origin of the shifted potential is explained based on spectroscopic, structural, and theoretical analyses of the iron(II) and iron(III) compounds.
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