X-ray absorption spectroscopy of a coordinatively unsaturated 3d transition metal complex
Year: 2025
Type: article
Abstract: Coordinatively unsaturated transition-metal complexes are employed as active catalysts in a wide range of homogeneous chemical reactions, including C-H bond activation. Because of their high reactivity and resulting affinity to rapidly bind substrate molecules, they are generally challenging to detect and characterize when prepared photochemically. Here, we generate the 16-electron cationic complex [CpFe(CO)2]+ (Cp = cyclopentadienyl) in the gas phase using electrospray ionization and probe its electronic structure with x-ray absorption spectroscopy at the Fe L-edge. Supported by multiconfigurational spectrum calculations, the distinct L-edge absorption profile of [CpFe(CO)2]+ reveals direct access to a low-lying unoccupied Fe 3d-derived orbital, which is characteristic of the unsaturated coordination of the complex and of its pronounced affinity to bind even notoriously unreactive moieties such as alkanes.
Source: The Journal of Chemical Physics
DOI: 10.1063/5.0303651
Language: English
Subfield: Radiation
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $3,500
Awards: G2178617979, Transforming strong bonds: Orbital-specific x-ay spectroscopy will tell us how to, Seeing clear where others can’t – X-rays uncover the birth of C-H activation catalysts and how they function, Soft x-ray spectroscopy for ultra-dilute in operando catalysts: Using machine learning for spectrometer developments, Time-resolved X-ray Stark Spectroscopy to Quantify Charge-Transfer in Chemical Reactions and Catalysis, Design principles for efficient metal-oxo catalysts revealed by x-rays, G7439578464, G965170539
OpenAlex ID: W4415930130