Detection and Characterization of Hydride Ligands in Copper Complexes by Hard X-Ray Spectroscopy.

ABSTRACT

Transition metal complexes, particularly copper hydrides, play an important role in various catalytic processes and molecular inorganic chemistry. This study employs synchrotron hard X-ray spectroscopy to gain insights into the geometric and electronic properties of copper hydrides as potential catalysts for CO2 hydrogenation. The potential of high energy resolution X-ray absorption near-edge structure (HERFD-XANES) and valence-to-core X-ray emission (VtC-XES) is demonstrated with measurement on Stryker's reagent (Cu6H6) and [Cu3(µ3-H)(dpmppe)2](PF6)2 (Cu3H), alongside a non-hydride copper compound ICu(dtbppOH) (Cuy-I). The XANES analysis reveals that coordination geometries strongly influence the spectra, providing only indirect details about hydride coordination. The VtC-XES analysis exhibits a distinct signal around 8975 eV, offering a diagnostic tool to identify hydride ligands. Theoretical calculations support and extend these findings by comparing hydride-containing complexes with their hydride-free counterparts.