Electronic Structure of the Hieber Anion [Fe(CO)₃(NO)]^- Revisited by X-ray Emission and Absorption Spectroscopy

While the Hieber anion [Fe(CO)₃(NO)]^- has been reincarnated in the last years as an active catalyst in organic synthesis, there is still a debate about the oxidation state of the central Fe atom and the resulting charge of the NO ligand. To shed new light on this question and to understand the Fe-NO interaction in the Hieber anion, it is investigated in comparison to the formal 3d⁸ reference Fe(CO)₅ and the formal 3d¹⁰ reference [Fe(CO)₄]^2- by the combination of valence-to-core X-ray emission spectroscopy (VtC-XES), X-ray absorption near-edge structure spectroscopy (XANES), and high-energy-resolution fluorescence-detected XANES. In order to extract information about the electronic structure, time-dependent density functional theory and ground-state density functional theory calculations are applied. This combination of experimental and computational methods reveals that the electron density at the Fe center of the Hieber resembles that of the isoelectronic [Fe(CO)₄]^2-. These observations challenge recent descriptions of the Hieber anion and reopen the debate about the experimentally and computationally determined Fe oxidation state and charge on the NO ligand.