Single‐Site Zeolite‐Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry |
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| Authors: | Claudia Martinez‐Macias Dr Mingyang Chen Prof David A Dixon Prof Bruce C Gates |
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| Institution: | 1. Department of Chemical Engineering and Materials Science, University of California, Davis, One Shields Avenue, Davis, California, 95616 (USA);2. Department of Chemistry, The University of Alabama, Tuscaloosa, Alabama, 35487 (USA);3. National Center for Computational Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee, 37831 (USA) |
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| Abstract: | A family of HY zeolite‐supported cationic organoiridium carbonyl complexes was formed by reaction of Ir(CO)2(acac) (acac=acetylacetonate) to form supported Ir(CO)2 complexes, which were treated at 298 K and 1 atm with flowing gas‐phase reactants, including C2H4, H2, 12CO, 13CO, 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. Because the support is crystalline and presents a nearly uniform array of bonding sites for the iridium species, 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. |
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| Keywords: | CO probe molecule DFT calculations iridium carbonyls iridium hydride zeolites |
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