Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

Handle URI:
http://hdl.handle.net/10754/575919
Title:
Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity
Authors:
Żukowska, Karolina; Pump, Eva; Pazio, Aleksandra E; Woźniak, Krzysztof; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Slugovc, Christian
Abstract:
Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity 2015, 11:1458 Beilstein Journal of Organic Chemistry
Publisher:
Beilstein Institut
Journal:
Beilstein Journal of Organic Chemistry
Issue Date:
20-Aug-2015
DOI:
10.3762/bjoc.11.158
Type:
Article
ISSN:
1860-5397
Additional Links:
http://www.beilstein-journals.org/bjoc/content/11/1/158
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC); KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorŻukowska, Karolinaen
dc.contributor.authorPump, Evaen
dc.contributor.authorPazio, Aleksandra Een
dc.contributor.authorWoźniak, Krzysztofen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorSlugovc, Christianen
dc.date.accessioned2015-08-25T07:58:49Zen
dc.date.available2015-08-25T07:58:49Zen
dc.date.issued2015-08-20en
dc.identifier.citationConsequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity 2015, 11:1458 Beilstein Journal of Organic Chemistryen
dc.identifier.issn1860-5397en
dc.identifier.doi10.3762/bjoc.11.158en
dc.identifier.urihttp://hdl.handle.net/10754/575919en
dc.description.abstractTwo ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.en
dc.language.isoenen
dc.publisherBeilstein Instituten
dc.relation.urlhttp://www.beilstein-journals.org/bjoc/content/11/1/158en
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 ) The definitive version of this article is the electronic one which can be found at: doi:10.3762/bjoc.11.158en
dc.subjectDFT calculationsen
dc.subjectolefin metathesisen
dc.subjectring closing metathesisen
dc.subjectring-opening metathesis polymerisationen
dc.subjectrutheniumen
dc.titleConsequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivityen
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.institutionInstitute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa, Polanden
dc.contributor.institutionInstitute of Chemistry and Technology of Materials, Graz University of Technology, NAWI Graz, Stremayrgasse 9, 8010 Graz, Austriaen
dc.contributor.institutionBiological and Chemical Research Centre, Faculty of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089; Warszawa, Polanden
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorCavallo, Luigien
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