Making oxidation potentials predictable: Coordination of additives applied to the electronic fine tuning of an iron(II) complex

Stefan Haslinger, Jens W. Kück, Eva M. Hahn, Mirza Cokoja, Alexander Pöthig, Jean-Marie Basset, Fritz Kühn

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

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.
Original languageEnglish (US)
Pages (from-to)11573-11583
Number of pages11
JournalInorganic Chemistry
Volume53
Issue number21
DOIs
StatePublished - Oct 21 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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