Show simple item record

dc.contributor.authorPump, Eva
dc.contributor.authorSlugovc, Christian
dc.contributor.authorCavallo, Luigi
dc.contributor.authorPoater, Albert
dc.date.accessioned2015-08-19T12:23:34Z
dc.date.available2015-08-19T12:23:34Z
dc.date.issued2015-06-30
dc.identifier.citationMechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis 2015, 34 (13):3107 Organometallics
dc.identifier.issn0276-7333
dc.identifier.issn1520-6041
dc.identifier.doi10.1021/om501246q
dc.identifier.urihttp://hdl.handle.net/10754/575254
dc.description.abstractThe intramolecular allenylidene RuCl2(PR3)2(C═C═CPh2) to indenylidene RuCl2(PR3)2(Ind) rearrangement that occurs during the synthesis of Ru-based precatalysts for olefin metathesis is presented. In the absence of acid, the ring closure via C–H activation was shown to be unfavored for energy barriers up to 70 kcal/mol. Thus, it turned out to be HCl (or other acid) that plays a crucial role during formation of the indenylidene, as the upper energy barrier decreases to a reasonable 35 kcal/mol. Moreover, we proved computationally that depending on the nature of the phosphine the intramolecular rearrangement is either facilitated (PPh3) or slightly hampered (PCy3), which is in line with experimental results.
dc.language.isoen
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/om501246q
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/om501246q.
dc.subjectOlefin Metathesis
dc.subjectMechanism
dc.subjectComputational studies
dc.subjectDFT
dc.subjectRuthenium
dc.subjectIndenylidene
dc.subjectAllenylidene
dc.titleMechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalOrganometallics
dc.eprint.versionPost-print
dc.contributor.institutionInstitute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, A-8010 Graz, Austria
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona, Catalonia, Spain
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)
kaust.personPump, Eva
kaust.personCavallo, Luigi
refterms.dateFOA2016-06-30T00:00:00Z
dc.date.published-online2015-06-30
dc.date.published-print2015-07-13


Files in this item

Thumbnail
Name:
Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangeme.pdf
Size:
330.1Kb
Format:
PDF
Description:
Accepted Manuscript

This item appears in the following Collection(s)

Show simple item record