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

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

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)

© Dalton Transactions, 2013, vol. 42, núm. 20, p. 7433-7439

Royal Society of Chemistry

Author: Poater Teixidor, Albert
Falivene, Laura
Urbina-Blanco, Cesar A.
Manzini, Simone
Nolan, Steven P.
Cavallo, Luigi
Date: 2013
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
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)
Format: application/pdf
ISSN: 1477-9226 (versió paper)
1477-9234 (versió electrònica)
Document access: http://hdl.handle.net/10256/8657
Language: eng
Publisher: Royal Society of Chemistry
Collection: MICINN/PN 2012-2015/RYC-2009-05226
AGAUR/2011BE100793
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c3dt32980a
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Dalton Transactions, 2013, vol. 42, núm. 20, p. 7433-7439
Rights: Tots els drets reservats
Subject: Ruteni -- Compostos
Ruthenium compounds
Density functionals
Funcional de densitat, Teoria del
Metàtesi (Química)
Metathesis (Chemistry)
Title: How does the addition of steric hindrance to a typical N-heterocyclic carbene ligand affect catalytic activity in olefin metathesis?
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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