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On the Mechanism of Ruthenium-Catalyzed Formation of Hydrogen from Alcohols: A DFT Study
Rhein Westfal TH Aachen, Inst Organ Chem.
2010 (Engelska)Ingår i: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 16, nr 45, s. 13487-13499Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

The mechanism of the ruthenium-catalyzed dehydrogenation of methanol has been investigated by using three DFT-based methods. Three pathways were considered in which the ruthenium catalyst was ligated by either two or three phosphine ligands. Dispersion interactions, which are not described by the popular B3LYP functional, were taken into account by using the dispersion-corrected B3LYP-D and M06 density functionals. These interactions were found to be important in the description of reaction steps that involved ligand/substrate/product association with or dissociation from the catalyst. In line with experimental results, the resting state of the catalyst was predicted to be a ruthenium trihydride complex. It is shown that the dehydrogenation reaction preferentially proceeds through pathways in which the catalyst is ligated by two phosphine ligands. The catalytic cycle of the dehydrogenation process involves an inter-molecular proton transfer from the methanol substrate to the catalyst followed by the release of dihydrogen. Rate-determining beta-hydride elimination from the resulting methoxide species then regenerates the resting state of the catalyst and completes the catalytic cycle. The overall free-energy barriers of 29.6-31.4 kcal mol(-1) predicted by the three density functionals are in good agreement with the experimentally observed reaction rate of 6 h(-1) at 423 K.

Ort, förlag, år, upplaga, sidor
2010. Vol. 16, nr 45, s. 13487-13499
Nyckelord [en]
dehydrogenation, dispersion interactions, hydrogen, reaction mechanisms, ruthenium
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Identifikatorer
URN: urn:nbn:se:kth:diva-77643DOI: 10.1002/chem.201000593ISI: 000285398400027OAI: oai:DiVA.org:kth-77643DiVA, id: diva2:491930
Anmärkning
QC 20120208Tillgänglig från: 2012-02-07 Skapad: 2012-02-07 Senast uppdaterad: 2017-12-08Bibliografiskt granskad

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Johansson, Adam Johannes
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