Valence‐to‐Core X‐Ray Emission Spectroscopy of Iron–Carbonyl Complexes: Implications for the Examination of Catalytic Intermediates |
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| Authors: | Mario Ulises Delgado‐Jaime Prof. Serena DeBeer Prof. Matthias Bauer |
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| Affiliation: | 1. Max‐Planck‐Institut für Chemische Energiekonversion, Stiftstrasse 34–36, 45470 Mülheim a.d.R. (Germany);2. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853 (USA);3. Fachbereich Chemie, Technische Universit?t Kaiserslautern, Erwin‐Schr?dinger‐Strasse 54, 67663 Kaiserslautern (Germany) |
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| Abstract: | Valence‐to‐core X‐ray emission spectroscopy (V2C XES) has been applied to a series of compounds relevant to both homogeneous catalysts and intermediates in heterogeneous reactions, namely [Fe(CO)5], [Fe2(CO)9], [Fe3(CO)12], [Fe(CO)3(cod)] (cod=cyclo‐octadienyl), [Fe2Cp2(CO)4] (Cp=cyclo‐pentadienyl), [Fe2Cp*2(CO)4] (Cp*=tetramethylcyclopentadienyl), and [FeCp(CO)2(thf)][B(ArF)4] (ArF=pentafluorophenyl). DFT calculations of the V2C XES spectra show very good agreement with experiment, which allows for an in depth analysis of the origins of the observed spectral signatures. It is demonstrated that the observed spectral features can be broken down into specific ligand and metal fragment contributions. The relative intensities of the observed features are further explained through a quantitative investigation of the metal 3p and 4p contributions to the spectra. The ability to use V2C XES to separate carbonyl, hydrocarbon, and solvent contributions is highlighted. |
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| Keywords: | catalysis density functional calculations emission spectroscopy iron carbonyls molecular orbitals |
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