Molecular models of site-isolated cobalt, rhodium, and iridium catalysts supported on zeolites: Ligand bond dissociation energies

Chen, Mingyang; Serna, Pedro; Lu, Jing; Gates, Bruce C.; Dixon, David A.

doi:10.1016/j.comptc.2015.09.004

Molecular models of site-isolated cobalt, rhodium, and iridium catalysts supported on zeolites: Ligand bond dissociation energies

Journal Article · Mon Sep 28 00:00:00 EDT 2015 · Computational and Theoretical Chemistry

DOI:https://doi.org/10.1016/j.comptc.2015.09.004· OSTI ID:1261491

Chen, Mingyang ^[1]; Serna, Pedro ^[2]; Lu, Jing ^[2]; Gates, Bruce C. ^[2]; Dixon, David A. ^[3]

Univ. of Alabama, Tuscaloosa, AL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of California, Davis, CA (United States)
Univ. of Alabama, Tuscaloosa, AL (United States)

The chemistry of zeolite-supported site-isolated cobalt, rhodium, and iridium complexes that are essentially molecular was investigated with density functional theory (DFT) and the results compared with experimentally determined spectra characterizing rhodium and iridium species formed by the reactions of Rh(C₂H₄)₂(acac) and Ir(C₂H₄)₂(acac) (acac = acetylacetonate) with acidic zeolites such as dealuminated HY zeolite. The experimental results characterize ligand exchange reactions and catalytic reactions of adsorbed ligands, including olefin hydrogenation and dimerization. Two molecular models were used to characterize various binding sites of the metal complexes in the zeolites, and the agreement between experimental and calculated infrared frequencies and metal-ligand distances determined by extended X-ray absorption fine structure spectroscopy was generally very good. The calculated structures and energies indicate a metal-support-oxygen (M(I)-O) coordination number of two for most of the supported complexes and a value of three when the ligands include the radicals C₂H₅ or H. The results characterizing various isomers of the supported metal complexes incorporating hydrocarbon ligands indicate that some carbene and carbyne ligands could form. Ligand bond dissociation energies (LDEs) are reported to explain the observed reactivity trends. The experimental observations of a stronger M-CO bond than M-(C₂H₄) bond for both Ir and Rh match the calculated LDEs, which show that the single-ligand LDEs of the mono and dual-ligand complexes for CO are similar to 12 and similar to 15 kcal/mol higher in energy (when the metal is Rh) and similar to 17 and similar to 20 kcal/mol higher (when the metal is Ir) than the single-ligand LDEs of the mono and dual ligand complexes for C₂H₄, respectively. The results provide a foundation for the prediction of the catalytic properties of numerous supported metal complexes, as summarized in detail here.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725; SC0005822

OSTI ID:: 1261491

Alternate ID(s):: OSTI ID: 1251802

Journal Information:: Computational and Theoretical Chemistry, Journal Name: Computational and Theoretical Chemistry Journal Issue: C Vol. 1074; ISSN 2210-271X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Molecular models of site-isolated cobalt, rhodium, and iridium catalysts supported on zeolites: Ligand bond dissociation energies

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