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Low-Valent Iron Mono-Diazadiene Compounds: Electronic Structure and Catalytic Application

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Department of Chemistry and Applied Biosciences, ETH Zürich, CH-8093 Zürich, Switzerland
Department of Chemistry & Pharmacy, Friedrich-Alexander University, Erlangen-Nürnberg (FAU), Egerlandstraße 1, D-91058 Erlangen, Germany
§ van ’t Hoff Institute for Molecular Sciences, Department of Homogeneous Catalysis, Faculty of Science, Universiteit van Amsterdam, Postbus 94720, 1090 GS Amsterdam, The Netherlands
*E-mail for C.L.: [email protected]
*E-mail for H.G.: [email protected]
Cite this: ACS Catal. 2015, 5, 10, 6230–6240
Publication Date (Web):September 15, 2015
https://doi.org/10.1021/acscatal.5b01416
Copyright © 2015 American Chemical Society

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    Abstract

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    A series of monodiazadiene diolefin iron compounds, [Fe(trop2dad)(L)] (4; L = neutral ligand), has been prepared by one-electron oxidation of the FeI species [NaFe(trop2dad)(thf)3] (dad = diazadiene; trop = 5H-dibenzo[a,d]cyclohepten-5-yl). The electronic structures of compounds 4 were investigated by NMR and Mössbauer spectroscopy, single-crystal X-ray diffraction, solid- and liquid-phase magnetic susceptibility measurements, and DFT calculations. Compounds of type 4 with labile ligands L were found to be active (pre)catalysts for the dehydrogenative coupling of (alkyl)amine–boranes. Remarkably high activities were observed, especially for the homogeneous dehydrogenative polymerization of methylamine–borane.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.5b01416.

    • Single-crystal X-ray analyses, Mössbauer spectroscopy, DFT calculations, isotropic shift analysis, and catalysis (PDF)

    • Crystallographic data for 1a (CIF)

    • Crystallographic data for 3 (CIF)

    • Crystallographic data for 4a (CIF)

    • Crystallographic data for 4b (CIF)

    • Crystallographic data for 4c (CIF)

    • Crystallographic data for 4d (CIF)

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