ic8b03032_si_001.pdf (933.58 kB)

The Bonding Situation in the Dinuclear Tetra-Hydrido Complex [{5CpFe}2(μ-H)4] Revisited by Hard X‑Ray Spectroscopy

Download (933.58 kB)
journal contribution
posted on 31.12.2018, 20:48 by Lukas Burkhardt, Carsten Mueller, Oliver A. Groß, Yu Sun, Helmut Sitzmann, Matthias Bauer
High energy resolution fluorescence detected XANES (HERFD-XANES) and valence-to-core X-ray emission spectroscopy (VtC-XES) are introduced as powerful tools to investigate hydride–iron interaction, the possible iron–iron bond, and iron spin state of the dinuclear tetra-hydrido complex [{5CpFe}2(μ-H)4] (1H, 5Cp = η5-C5iPr5) by thoroughly accessing the geometric and electronic structure of this complex in comparison to the nonhydride reference [5CpCpFe] (1, Cp = C5H5). The so far observed most intense hydride induced signals in the pre-edge feature of the HERFD-XANES and in the VtC-XES spectra at the iron K-edge allow a precise analysis of the LUMO and HOMO states, respectively, by application of time-dependent density function theory (TD-DFT) and density functional theory (DFT) calculations. The results of these calculations are further employed to understand the oxidation state, spin states, and potential Fe–Fe bonds in this complex.