Can Contemporary Density Functional Theory Predict Energy Spans in Molecular Catalysis Accurately Enough To Be Applicable for in Silico Catalyst Design? A Computational/Experimental Case Study for the Ruthenium-Catalyzed Hydrogenation of Olefins.
The catalytic hydrogenation of cyclohexene and 1-methylcyclohexene is investigated experimentally and by means of density functional theory (DFT) computations using novel ruthenium Xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) and Xantphos (4,5-bis(dicyclohexylphosphino)-9,9-dimethylxan...
| Publicado en: | Journal of the American Chemical Society Vol. 138; no. 1; pp. 433 - 444 |
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| Autores principales: | , , |
| Formato: | Artículo |
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American Chemical Society
1/13/2016
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=113302255&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 113302255 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 1/13/2016 vid: 138 iid: 1 pid: 997 pub: American Chemical Society artinfo: ui: 113302255 10.1021/jacs.5b11997 ppf: 433 ppct: 11 formats: tig: atl: Can Contemporary Density Functional Theory Predict Energy Spans in Molecular Catalysis Accurately Enough To Be Applicable for in Silico Catalyst Design? A Computational/Experimental Case Study for the Ruthenium-Catalyzed Hydrogenation of Olefins. aug: au: Rohmann, Kai Hölscher, Markus Leitner, Walter affil: Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2, 52074 Aachen, Germany Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim a.d. Ruhr, Germany su: Density functional theory Ruthenium catalysts Hydrogenation Alkenes Cyclohexene Gibbs' equation sug: subj: Density functional theory Ruthenium catalysts Hydrogenation Alkenes Cyclohexene Gibbs' equation ab: The catalytic hydrogenation of cyclohexene and 1-methylcyclohexene is investigated experimentally and by means of density functional theory (DFT) computations using novel ruthenium Xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) and Xantphos (4,5-bis(dicyclohexylphosphino)-9,9-dimethylxanthene) precatalysts [Ru(Xantphos)(PhCO)(Cl)] () and [Ru(Xantphos)(PhCO)(Cl)] (), the synthesis, characterization, and crystal structures of which are reported. The intention of this work is to (i) understand the reaction mechanisms on the microscopic level and (ii) compare experimentally observed activation barriers with computed barriers. The Gibbs free activation energy ΔG was obtained experimentally with precatalyst from Eyring plots for the hydrogenation of cyclohexene (ΔG = 17.2 ± 1.0 kcal/mol) and 1-methylcyclohexene (ΔG = 18.8 ± 2.4 kcal/mol), while the Gibbs free activation energy ΔG for the hydrogenation of cyclohexene with precatalyst was determined to be 21.1 ± 2.3 kcal/mol. Plausible activation pathways and catalytic cycles were computed in the gas phase (M06-L/def2-SVP). A variety of popular density functionals (ωB97X-D, LC-ωPBE, CAM-B3LYP, B3LYP, B97-D3BJ, B3LYP-D3, BP86-D3, PBE0-D3, M06-L, MN12-L) were used to reoptimize the turnover determining states in the solvent phase (DF/def2-TZVP; IEF-PCM and/or SMD) to investigate how well the experimentally obtained activation barriers can be reproduced by the calculations. The density functionals B97-D3BJ, MN12-L, M06-L, B3LYP-D3, and CAM-B3LYP reproduce the experimentally observed activation barriers for both olefins very well with very small (0.1 kcal/mol) to moderate (3.0 kcal/mol) mean deviations from the experimental values indicating for the field of hydrogenation catalysis most of these functionals to be useful for in silico catalyst design prior to experimental work. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2016 holdings: @attributes: islocal: N |
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