How does the addition of steric hindrance to a typical N-heterocyclic carbene ligand affect catalytic activity in olefin metathesis?

Handle URI:
http://hdl.handle.net/10754/562485
Title:
How does the addition of steric hindrance to a typical N-heterocyclic carbene ligand affect catalytic activity in olefin metathesis?
Authors:
Poater, Albert; Falivene, Laura; Urbina-Blanco, César A.; Manzini, Simone; Nolan, Steven P.; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
Density functional theory (DFT) calculations were used to predict and rationalize the effect of the modification of the structure of the prototype 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) N-heterocyclic carbene (NHC) ligand. The modification consists in the substitution of the methyl groups of ortho isopropyl substituent with phenyl groups, and here we plan to describe how such significant changes affect the metal environment and therefore the related catalytic behaviour. Bearing in mind that there is a significant structural difference between both ligands in different olefin metathesis reactions, here by means of DFT we characterize where the NHC ligand plays a more active role and where it is a simple spectator, or at least its modification does not significantly change its catalytic role/performance. © 2013 The Royal Society of Chemistry.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Dalton Transactions
Issue Date:
2013
DOI:
10.1039/c3dt32980a
Type:
Article
ISSN:
14779226
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. A. P. and L. C. thank 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. A. P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226), European Commission for a Career Integration Grant (CIG09-GA-2011-293900), and Generalitat de Catalunya (2011BE100793). SPN is a Royal Society Wolfson Research Merit Award holder.
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.authorPoater, Alberten
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorUrbina-Blanco, César A.en
dc.contributor.authorManzini, Simoneen
dc.contributor.authorNolan, Steven P.en
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-08-03T10:39:50Zen
dc.date.available2015-08-03T10:39:50Zen
dc.date.issued2013en
dc.identifier.issn14779226en
dc.identifier.doi10.1039/c3dt32980aen
dc.identifier.urihttp://hdl.handle.net/10754/562485en
dc.description.abstractDensity functional theory (DFT) calculations were used to predict and rationalize the effect of the modification of the structure of the prototype 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) N-heterocyclic carbene (NHC) ligand. The modification consists in the substitution of the methyl groups of ortho isopropyl substituent with phenyl groups, and here we plan to describe how such significant changes affect the metal environment and therefore the related catalytic behaviour. Bearing in mind that there is a significant structural difference between both ligands in different olefin metathesis reactions, here by means of DFT we characterize where the NHC ligand plays a more active role and where it is a simple spectator, or at least its modification does not significantly change its catalytic role/performance. © 2013 The Royal Society of Chemistry.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. A. P. and L. C. thank 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. A. P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226), European Commission for a Career Integration Grant (CIG09-GA-2011-293900), and Generalitat de Catalunya (2011BE100793). SPN is a Royal Society Wolfson Research Merit Award holder.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.titleHow does the addition of steric hindrance to a typical N-heterocyclic carbene ligand affect catalytic activity in olefin metathesis?en
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalDalton Transactionsen
dc.contributor.institutionInstitut de Química Computacional, Departament de Química, Universitat de Girona, E-17071 Girona, Catalonia, Spainen
dc.contributor.institutionDipartimento di Chimica e Biologia, Università di Salerno, Via Ponte don Melillo, 84084 Fisciano, Italyen
dc.contributor.institutionEaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, United Kingdomen
kaust.authorCavallo, Luigien
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