Making oxidation potentials predictable: Coordination of additives applied to the electronic fine tuning of an iron(II) complex
Kück, Jens W.
Hahn, Eva M.
KAUST DepartmentKAUST Catalysis Center (KCC)
Physical Sciences and Engineering (PSE) Division
Chemical Science Program
Permanent link to this recordhttp://hdl.handle.net/10754/563842
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AbstractThis 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.
SponsorsThis work is based on funding by Award KSA-00069/UK-C0020, made by KAUST. The authors gratefully acknowledge the Gauss Centre for Supercomputing eV for funding this project by providing computing time on the GCS Supercomputer SuperMUC at Leibniz Supercomputing Centre, and the TUM-GS is acknowledged for support. J.W.K. thanks the Studienstiftung des Deutsdien Volkes for support, and S.H. is thankful to Maike H. Wahl for her valuable contributions.
PublisherAmerican Chemical Society (ACS)