Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis

Handle URI:
http://hdl.handle.net/10754/575254
Title:
Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis
Authors:
Pump, Eva ( 0000-0003-2810-2546 ) ; Slugovc, Christian; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Poater, Albert
Abstract:
The 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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis 2015, 34 (13):3107 Organometallics
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
Issue Date:
30-Jun-2015
DOI:
10.1021/om501246q
Type:
Article
ISSN:
0276-7333; 1520-6041
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/om501246q
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPump, Evaen
dc.contributor.authorSlugovc, Christianen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorPoater, Alberten
dc.date.accessioned2015-08-19T12:23:34Zen
dc.date.available2015-08-19T12:23:34Zen
dc.date.issued2015-06-30en
dc.identifier.citationMechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis 2015, 34 (13):3107 Organometallicsen
dc.identifier.issn0276-7333en
dc.identifier.issn1520-6041en
dc.identifier.doi10.1021/om501246qen
dc.identifier.urihttp://hdl.handle.net/10754/575254en
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.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/om501246qen
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.en
dc.subjectOlefin Metathesisen
dc.subjectMechanismen
dc.subjectComputational studiesen
dc.subjectDFTen
dc.subjectRutheniumen
dc.subjectIndenylideneen
dc.subjectAllenylideneen
dc.titleMechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesisen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalOrganometallicsen
dc.eprint.versionPost-printen
dc.contributor.institutionInstitute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, A-8010 Graz, Austriaen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona, Catalonia, Spainen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorPump, Evaen
kaust.authorCavallo, Luigien
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