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Title: Single-Site Zeolite-Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry

We formed a family of HY zeolite-supported cationic organoiridium carbonyl complexes by reaction of Ir(CO)2(acac) (acac=acetylacetonate) to form supported Ir(CO)2 complexes, which were treated at 298K and 1atm with flowing gas-phase reactants, including C2H4, H2, (CO)-C-12, (CO)-C-13, and D2O. Mass spectrometry was used to identify effluent gases, and infrared and X-ray absorption spectroscopies were used to characterize the supported species, with the results bolstered by DFT calculations. The support is crystalline and presents a nearly uniform array of bonding sites for the iridium species, so these were characterized by a high degree of uniformity, which allowed a precise determination of the species involved in the replacement, for example, of one CO ligand of each Ir(CO)2 complex with ethylene. The supported species include the following: Ir(CO)2, Ir(CO)(C2H4)2, Ir(CO)(C2H4), Ir(CO)(C2H5), and (tentatively) Ir(CO)(H). The data determine a reaction network involving all of these species.
Authors:
 [1] ;  [2] ;  [3] ;  [1]
  1. Univ. of California, Davis, CA (United States)
  2. Univ. of Alabama, Tuscaloosa, AL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Alabama, Tuscaloosa, AL (United States)
Publication Date:
OSTI Identifier:
1261461
Grant/Contract Number:
AC05-00OR22725; FG02-04ER15513; SC0005822; AC02-06CH11357; NA0001974; FG02-99ER45775; AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 21; Journal Issue: 33; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Research Org:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY CO probe molecule; DFT calculations; iridium carbonyls; iridium hydride; zeolites; RELATIVISTIC EFFECTIVE POTENTIALS; DEALUMINATED Y-ZEOLITE; SPIN-ORBIT OPERATORS; IRIDIUM COMPLEXES; CO; CATALYSTS; CLUSTERS; SUPPORTS; DENSITY; HYDROGENATION