Intact and fragmented triosmium clusters on MgO: Characterization by X-ray absorption spectroscopy and high-resolution transmission electron microscopy

Oxidative fragmentation of the clusters Os-3(CO)(12) adsorbed on MgO powder was investigated by X-ray absorption spectroscopy and scanning transmission electron microscopy (STEM). Exposure of the clusters to air leads to their fragmentation, oxidation of the osmium, and formation of ensembles consisting of three Os atoms. X-ray absorption near-edge spectra demonstrate the oxidative nature of the fragmentation process. Extended X-ray absorption fine structure (EXAFS) spectra indicate an average Os-Os distance of 3.33 angstrom and an Os-Os coordination number of 2, consistent with the formation of ensembles of three Os atoms on the support. STEM images confirm the presence of such trinuclear ensembles, and the diameters of the observed scattering centers (6.0 angstrom) match that indicated by the EXAFS results.