title: Making oxidation potentials predictable: coordination of additives applied to the electronic fine tuning of an iron(II) complex.
abstract: This work examines the impact of axially coordinating additives on the electronic structure of a bioinspired octahedral low-spin iron(II) N-heterocyclic carbene (Fe-NHC) complex. Bearing two labile trans-acetonitrile ligands, the Fe-NHC complex, which is also an excellent oxidation catalyst, is prone to axial ligand exchange. Phosphine- and pyridine-based additives are used for substitution of the acetonitrile ligands. On the basis of the resulting defined complexes, predictability of the oxidation potentials is demonstrated, based on a correlation between cyclic voltammetry experiments and density functional theory calculated molecular orbital energies. Fundamental insights into changes of the electronic properties upon axial ligand exchange and the impact on related attributes will finally lead to target-oriented manipulation of the electronic properties and consequently to the effective tuning of the reactivity of bioinspired systems.
authors.affiliation: Inorganic Chemistry/Molecular Catalysis, Catalysis Research Center, Technische Universität München (TUM) , Ernst-Otto-Fischer-Straße 1, 85747 Garching bei München, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Haslinger
authors.forename: Jens W
authors.initials: JW
authors.lastname: Kück
authors.forename: Eva M
authors.initials: EM
authors.lastname: Hahn
authors.forename: Mirza
authors.initials: M
authors.lastname: Cokoja
authors.forename: Alexander
authors.initials: A
authors.lastname: Pöthig
authors.forename: Jean-Marie
authors.initials: JM
authors.lastname: Basset
authors.forename: Fritz E
authors.initials: FE
authors.lastname: Kühn
mesh_terms: D004583:Electrons; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D011789:Quantum Theory
chemical_list: D005296:Ferrous Compounds; D008024:Ligands