@article{a740ab4694d046bcb84d01260ca149c8,
title = "Tuning the Fe(II/III) Redox Potential in Nonheme Fe(II)-Hydroxo Complexes through Primary and Secondary Coordination Sphere Modifications",
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{\textquoteright} 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.",
author = "Zachary Gordon and Drummond, {Michael J.} and Matson, {Ellen M.} and Bogart, {Justin A.} and Schelter, {Eric J.} and Lord, {Richard L.} and Fout, {Alison R.}",
note = "Funding Information: This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division under award DE-SC-0016026 and the University of Illinois at Urbana−Champaign. Z.G. and A.R.F. thank Dr. Monte Helm for help with interpretation of electrochemical experiments. A.R.F. is grateful for an Alfred P. Sloan Fellowship. R.L.L. acknowledges financial support from the Research Foundation (Cottrell College Science Award) and computational resources provided by NSF-MRI award CHE-1039925 through the Midwest Undergraduate Computational Chemistry Consortium. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",
year = "2017",
month = may,
day = "1",
doi = "10.1021/acs.inorgchem.6b03071",
language = "English (US)",
volume = "56",
pages = "4852--4863",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "9",
}