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' 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.
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign , 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
authors.forename: Zachary
authors.initials: Z
authors.lastname: Gordon
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign , 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Drummond
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign , 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
authors.forename: Ellen M
authors.initials: EM
authors.lastname: Matson
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34 Street, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Justin A
authors.initials: JA
authors.lastname: Bogart
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34 Street, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Eric J
authors.identifier: http://orcid.org/0000-0002-8143-6206
authors.initials: EJ
authors.lastname: Schelter
authors.affiliation: Department of Chemistry, Grand Valley State University , 1 Campus Drive, Allendale, Michigan 49401, United States.
authors.forename: Richard L
authors.identifier: http://orcid.org/0000-0001-6692-0369
authors.initials: RL
authors.lastname: Lord
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign , 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
authors.forename: Alison R
authors.identifier: http://orcid.org/0000-0002-4669-5835
authors.initials: AR
authors.lastname: Fout