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2004-03-25Zeitschriftenartikel DOI: 10.1002/poc.842
Catalytic dehydrogenation of ethane over mononuclear Cr(III) surface sites on silica. part I. C - H activation by σ-bond metathesis
dc.contributor.authorLillehaug, Sindre
dc.contributor.authorBørve, Knut J.
dc.contributor.authorSierka, Marek
dc.contributor.authorSauer, Joachim
dc.date.accessioned2017-06-17T00:06:51Z
dc.date.available2017-06-17T00:06:51Z
dc.date.created2005-11-28
dc.date.issued2004-03-25
dc.date.submitted2004-10-01
dc.identifier.urihttp://edoc.hu-berlin.de/18452/9780
dc.description.abstractMononuclear Cr(III)-silica models have been studied by quantum chemical methods with respect to catalytic activity toward dehydrogenation of ethane. Both cluster and slab models have been developed and used to explore the conceptual model of mononuclear Cr(III) with three covalent ligands that coordinate through oxygen. The study focuses on a reaction mechanism consisting of three main reaction steps: (1) C - H activation of ethane according to -bond metathesis and accompanied by the formation of O - H and Cr - C bonds, (2) -H transfer to chromium with subsequent loss of ethene and (3) regeneration of the chromium site under evolution of H2. An alternative mechanism is also explored, in which C - H activation takes place at a reactive hydridochromium complex. Stationary points pertaining to these reactions have been optimized, and free energy calculations are used to identify the rate-determining steps. The influence of the local structure of the chromium surface sites is explored by means of a number of idealized surface models and electronic energy profiles for the reactions.eng
dc.language.isoeng
dc.publisherHumboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, Institut für Chemie
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/
dc.subjectDFTeng
dc.subjectreaction mechanismeng
dc.subjectCr-oxide catalysteng
dc.subjectsilicaeng
dc.subjectethaneeng
dc.subjectCH-activationeng
dc.subjectdehydrogenationeng
dc.subjectQMMMeng
dc.subjectclustereng
dc.subject.ddc540 Chemie
dc.titleCatalytic dehydrogenation of ethane over mononuclear Cr(III) surface sites on silica. part I. C - H activation by σ-bond metathesis
dc.typearticle
dc.identifier.urnurn:nbn:de:kobv:11-10054316
dc.identifier.doi10.1002/poc.842
dc.identifier.doihttp://dx.doi.org/10.18452/9128
local.edoc.container-titleJournal of Physical Organic Chemistry
local.edoc.type-nameZeitschriftenartikel
local.edoc.institutionInstitut für Chemie
local.edoc.container-typeperiodical
local.edoc.container-type-nameZeitschrift
local.edoc.container-eventconference
local.edoc.container-eventconference
local.edoc.container-volume2004
local.edoc.container-volume17
local.edoc.container-volume17
local.edoc.container-issue11
local.edoc.container-issue11
local.edoc.container-year2004
local.edoc.container-firstpage990
local.edoc.container-lastpage1006
dc.description.versionPeer Reviewed

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