A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

Handle URI:
http://hdl.handle.net/10754/579154
Title:
A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts
Authors:
Poater, Albert; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts 2015, 11:1767 Beilstein Journal of Organic Chemistry
Publisher:
Beilstein Institut
Journal:
Beilstein Journal of Organic Chemistry
Issue Date:
29-Sep-2015
DOI:
10.3762/bjoc.11.192
Type:
Article
ISSN:
1860-5397
Additional Links:
http://www.beilstein-journals.org/bjoc/content/11/1/192
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPoater, Alberten
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-10-04T12:14:01Zen
dc.date.available2015-10-04T12:14:01Zen
dc.date.issued2015-09-29en
dc.identifier.citationA comprehensive study of olefin metathesis catalyzed by Ru-based catalysts 2015, 11:1767 Beilstein Journal of Organic Chemistryen
dc.identifier.issn1860-5397en
dc.identifier.doi10.3762/bjoc.11.192en
dc.identifier.urihttp://hdl.handle.net/10754/579154en
dc.description.abstractDuring a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.en
dc.language.isoenen
dc.publisherBeilstein Instituten
dc.relation.urlhttp://www.beilstein-journals.org/bjoc/content/11/1/192en
dc.rightsThis is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (http://www.beilstein-journals.org/bjoc)en
dc.subjectcisen
dc.subjectdensity functional theory (DFT)en
dc.subjectN-heterocyclic carbeneen
dc.subjectolefin metathesisen
dc.subjectrutheniumen
dc.titleA comprehensive study of olefin metathesis catalyzed by Ru-based catalystsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalBeilstein Journal of Organic Chemistryen
dc.eprint.versionPublisher's Version/PDFen
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.authorCavallo, Luigien
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