Observations of Ethylene-for-CO Ligand Exchanges on a Zeolite-Supported Single-Site Rh Catalyst by X-ray Absorption Spectroscopy.

Quick-scanning X-ray absorption fine structure (QXAFS) measurements were used to characterize the exchanges of ethylene and CO ligands in a zeolite HY-supported single-site Rh complex at a sampling rate of 1.0 Hz. The two ligands were reversibly exchanged on the rhodium, with quantitative results determined for the CH-for-CO exchange that are consistent with a first-order process. The apparent rate constant for the exchange decreased with increasing temperature. Fourier-transform infrared spectra characterizing the CH sorbed in the zeolite showed that the amount decreased with increasing temperature, consistent with the decrease in the exchange rate with increasing temperature. The results, illustrating the dynamics of ligand exchanges on a single-site supported metal catalyst, demonstrate the broad emerging applicability of the QXAFS technique for characterizing the dynamics of reactive intermediates on catalysts.