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  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

Rohmann, K., Hölscher, M., & Leitner, W. (2016). 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. Journal of the American Chemical Society, 138(1), 433-443. doi:10.1021/jacs.5b11997.

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Rohmann, Kai1, Author
Hölscher, Markus1, Author
Leitner, Walter1, 2, Author           
Affiliations:
1Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2, 52074 Aachen, Germany, ou_persistent22              
2Research Group Leitner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445610              

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 Abstract: The catalytic hydrogenation of cyclohexene and 1-methylcyclohexene is investigated experimentally and by means of density functional theory (DFT) computations using novel ruthenium XantphosPh(4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) and XantphosCy (4,5-bis(dicyclohexylphosphino)-9,9-dimethylxanthene) precatalysts [Ru(XantphosPh)(PhCO2)(Cl)] (1) and [Ru(XantphosCy)(PhCO2)(Cl)] (2), 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 1 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 2 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.

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Language(s): eng - English
 Dates: 2015-12-292016-01-13
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.5b11997
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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 138 (1) Sequence Number: - Start / End Page: 433 - 443 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870