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

Handle URI:
http://hdl.handle.net/10754/563842
Title:
Making oxidation potentials predictable: Coordination of additives applied to the electronic fine tuning of an iron(II) complex
Authors:
Haslinger, Stefan; Kück, Jens W.; Hahn, Eva M.; Cokoja, Mirza; Pöthig, Alexander; Basset, Jean-Marie ( 0000-0003-3166-8882 ) ; Kühn, Fritz
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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society (ACS)
Journal:
Inorganic Chemistry
Issue Date:
3-Nov-2014
DOI:
10.1021/ic501613a
Type:
Article
ISSN:
00201669
Sponsors:
This 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.
Is Supplemented By:
Haslinger, S., Kück, J. W., Hahn, E. M., Cokoja, M., Pöthig, A., Basset, J.-M., & Kühn, F. E. (2015). CCDC 992643: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc129xr1; DOI:10.5517/cc129xr1; HANDLE:http://hdl.handle.net/10754/624305; Haslinger, S., Kück, J. W., Hahn, E. M., Cokoja, M., Pöthig, A., Basset, J.-M., & Kühn, F. E. (2015). CCDC 992644: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc129xs2; DOI:10.5517/cc129xs2; HANDLE:http://hdl.handle.net/10754/624306; Haslinger, S., Kück, J. W., Hahn, E. M., Cokoja, M., Pöthig, A., Basset, J.-M., & Kühn, F. E. (2015). CCDC 992645: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc129xt3; DOI:10.5517/cc129xt3; HANDLE:http://hdl.handle.net/10754/624307; Haslinger, S., Kück, J. W., Hahn, E. M., Cokoja, M., Pöthig, A., Basset, J.-M., & Kühn, F. E. (2015). CCDC 992646: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc129xv4; DOI:10.5517/cc129xv4; HANDLE:http://hdl.handle.net/10754/624308
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorHaslinger, Stefanen
dc.contributor.authorKück, Jens W.en
dc.contributor.authorHahn, Eva M.en
dc.contributor.authorCokoja, Mirzaen
dc.contributor.authorPöthig, Alexanderen
dc.contributor.authorBasset, Jean-Marieen
dc.contributor.authorKühn, Fritzen
dc.date.accessioned2015-08-03T12:16:33Zen
dc.date.available2015-08-03T12:16:33Zen
dc.date.issued2014-11-03en
dc.identifier.issn00201669en
dc.identifier.doi10.1021/ic501613aen
dc.identifier.urihttp://hdl.handle.net/10754/563842en
dc.description.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.en
dc.description.sponsorshipThis 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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleMaking oxidation potentials predictable: Coordination of additives applied to the electronic fine tuning of an iron(II) complexen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalInorganic Chemistryen
dc.contributor.institutionInorganic Chemistry/Molecular Catalysis, Catalysis Research Center, Technische Universität München (TUM), Ernst-Otto-Fischer-Straße 1Garching bei München, Germanyen
kaust.authorBasset, Jean-Marieen
dc.relation.isSupplementedByHaslinger, S., Kück, J. W., Hahn, E. M., Cokoja, M., Pöthig, A., Basset, J.-M., & Kühn, F. E. (2015). CCDC 992643: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc129xr1en
dc.relation.isSupplementedByDOI:10.5517/cc129xr1en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624305en
dc.relation.isSupplementedByHaslinger, S., Kück, J. W., Hahn, E. M., Cokoja, M., Pöthig, A., Basset, J.-M., & Kühn, F. E. (2015). CCDC 992644: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc129xs2en
dc.relation.isSupplementedByDOI:10.5517/cc129xs2en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624306en
dc.relation.isSupplementedByHaslinger, S., Kück, J. W., Hahn, E. M., Cokoja, M., Pöthig, A., Basset, J.-M., & Kühn, F. E. (2015). CCDC 992645: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc129xt3en
dc.relation.isSupplementedByDOI:10.5517/cc129xt3en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624307en
dc.relation.isSupplementedByHaslinger, S., Kück, J. W., Hahn, E. M., Cokoja, M., Pöthig, A., Basset, J.-M., & Kühn, F. E. (2015). CCDC 992646: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc129xv4en
dc.relation.isSupplementedByDOI:10.5517/cc129xv4en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624308en
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