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The Activation Mechanism of Ru-Indenylidene Complexes in Olefin Metathesis

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

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)

© Journal of the American Chemical Society, 2013, vol. 135, núm. 18, p. 7073-7079

American Chemical Society

Author: Urbina-Blanco, Cesar A.
Poater Teixidor, Albert
Lebl, Tomas
Manzini, Simone
Slawin, Alexandra M. Z.
Cavallo, Luigi
Nolan, Steven P.
Date: 2013
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
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)
Format: application/pdf
ISSN: 0002-7863 (versió paper)
1520-5126 (versió electrònica)
Document access: http://hdl.handle.net/10256/8649
Language: eng
Publisher: American Chemical Society
Collection: MICINN/PN 2012-2015/RYC-2009-05226
AGAUR/2012BE100824
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ja402700p
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Journal of the American Chemical Society, 2013, vol. 135, núm. 18, p. 7073-7079
Rights: Tots els drets reservats
Subject: Catàlisi
Catalysis
Ruteni -- Compostos
Ruthenium compounds
Activació (Química)
Activation (Chemistry)
Title: The Activation Mechanism of Ru-Indenylidene Complexes in Olefin Metathesis
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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