A site-isolated mononuclear iridium complex catalyst supported on MgO: Characterization by spectroscopy and aberration-corrected scanning transmission electron microscopy

Supported mononuclear iridium complexes with ethene ligands were prepared by the reaction of Ir(C2H4)(2)(acac) (acac is CH3CCCHCOCH3) wit:h highly dehydroxylated MgO. Characterization of the supported species by extended X-ray absorption fine structure (EXAFS) and infrared (IR) spectroscopies showed that the resultant supported organometallic species were Ir(C2H4)(2), formed by the dissociation of the acac ligand from Ir(C2H4)(2)(acac) and bonding of the Ir(C2H4)(2) species to the MgO surface. Direct evidence of the site-isolation of these mononuclear complexes was obtained by aberration-corrected scanning transmission electron microscopy (STEM); the images demonstrate the presence of the iridium complexes in the absence of any clusters. When the iridium complexes were probed with CO, the resulting IR spectra demonstrated the formation of Ir(CO)(2) complexes On the MgO surface. The breadth of the nu(CO) bands demonstrates a substantial variation in the metal-support bonding, consistent with the heterogeneity of the MgO surface; the STEM images are not sufficient to characterize this heterogeneity. The supported iridium complexes catalyzed ethene hydrogenation at room temperature and atmospheric pressure in a flow reactor, and EXAFS spectra indicated that the mononuclear iridium species remained intact. STEM images of the used catalyst confirmed that almost all of the iridium complexes remained intact, but this method was sensitive enough to detect a small degree of aggregation of the iridium on the support. (C) 2009 Published by Elsevier Inc.