The activation mechanism of Ru-indenylidene complexes in olefin metathesis

Handle URI:
http://hdl.handle.net/10754/562761
Title:
The activation mechanism of Ru-indenylidene complexes in olefin metathesis
Authors:
Urbina-Blanco, César A.; Poater, Albert; Lébl, Tomáš; Manzini, Simone; Slawin, Alexandra M. Z.; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Nolan, Steven P.
Abstract:
Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society
Journal:
Journal of the American Chemical Society
Issue Date:
8-May-2013
DOI:
10.1021/ja402700p
PubMed ID:
23617632
Type:
Article
ISSN:
00027863
Sponsors:
The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement no CP-FP 211468-2 EUMET. SPN is a Royal Society Wolfson Research Merit Award holder. LC thanks BSC (QCM-2010-2-0020), and the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. AP thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226), Generalitat de Catalunya (2012BE100824) and European Commission for a Career Integration Grant (CIG09-GA-2011-293900). Dr Julie Broggi is greatly acknowledged for preliminary research leading to this publication, Dr David J. Nelson and Prof. Fernando Febres Cordero are greatly acknowledged for helpful discussions. Umicore is greatly acknowledged for their generous donation of materials.
Is Supplemented By:
Urbina-Blanco, C. A., Poater, A., Lebl, T., Manzini, S., Broggi, J., Slawin, A. M. Z., … Nolan, S. P. (2014). CCDC 887969: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccyt05x; DOI:10.5517/ccyt05x; HANDLE:http://hdl.handle.net/10754/624723; Urbina-Blanco, C. A., Poater, A., Lebl, T., Manzini, S., Broggi, J., Slawin, A. M. Z., … Nolan, S. P. (2014). CCDC 887968: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccyt04w; DOI:10.5517/ccyt04w; HANDLE:http://hdl.handle.net/10754/624722
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorUrbina-Blanco, César A.en
dc.contributor.authorPoater, Alberten
dc.contributor.authorLébl, Tomášen
dc.contributor.authorManzini, Simoneen
dc.contributor.authorSlawin, Alexandra M. Z.en
dc.contributor.authorCavallo, Luigien
dc.contributor.authorNolan, Steven P.en
dc.date.accessioned2015-08-03T11:04:46Zen
dc.date.available2015-08-03T11:04:46Zen
dc.date.issued2013-05-08en
dc.identifier.issn00027863en
dc.identifier.pmid23617632en
dc.identifier.doi10.1021/ja402700pen
dc.identifier.urihttp://hdl.handle.net/10754/562761en
dc.description.abstractOlefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.en
dc.description.sponsorshipThe research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement no CP-FP 211468-2 EUMET. SPN is a Royal Society Wolfson Research Merit Award holder. LC thanks BSC (QCM-2010-2-0020), and the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. AP thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226), Generalitat de Catalunya (2012BE100824) and European Commission for a Career Integration Grant (CIG09-GA-2011-293900). Dr Julie Broggi is greatly acknowledged for preliminary research leading to this publication, Dr David J. Nelson and Prof. Fernando Febres Cordero are greatly acknowledged for helpful discussions. Umicore is greatly acknowledged for their generous donation of materials.en
dc.publisherAmerican Chemical Societyen
dc.titleThe activation mechanism of Ru-indenylidene complexes in olefin metathesisen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalJournal of the American Chemical Societyen
dc.contributor.institutionEaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St.Andrews-Fife, KY16 9ST, United Kingdomen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi, Departament de Química, University of Girona, 17071 Girona, Catalonia, Spainen
dc.contributor.institutionDepartment of Chemistry and Biology, University of Salerno, Via Ponte don Melillo, Fisciano I-84084, Italyen
kaust.authorCavallo, Luigien
dc.relation.isSupplementedByUrbina-Blanco, C. A., Poater, A., Lebl, T., Manzini, S., Broggi, J., Slawin, A. M. Z., … Nolan, S. P. (2014). CCDC 887969: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccyt05xen
dc.relation.isSupplementedByDOI:10.5517/ccyt05xen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624723en
dc.relation.isSupplementedByUrbina-Blanco, C. A., Poater, A., Lebl, T., Manzini, S., Broggi, J., Slawin, A. M. Z., … Nolan, S. P. (2014). CCDC 887968: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccyt04wen
dc.relation.isSupplementedByDOI:10.5517/ccyt04wen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624722en

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