Royal Society of Chemistry, Physical Chemistry Chemical Physics, 21(17), p. 13937-13948
DOI: 10.1039/c5cp01045d
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We apply high-energy-resolution fluorescence-detected (HERFD) X-ray absorption near-edge spectroscopy (XANES) to study iron carbonyl complexes. Mono-, bi, and trinuclear carbonyl complexes and pure carbonyl complexes as well as carbonyl complexes containing hydrocarbon ligands are considered. The HERFD-XANES spectra reveal multiple pre-edge peaks with individual signatures for each complex, which could not be detected previously with conventional XANES spectroscopy. These peaks are assigned and analysed with the help of TD-DFT calculations. We demonstrate that the pre-edge peaks can be used to distinguish the different types of iron--iron interactions in carbonyl complexes. This opens up new possibilities for applying HERFD-XANES spectroscopy to probe the electronic structure of iron catalysts.