Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity
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 a...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2015-08-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.11.158 |
| _version_ | 1819178970917109760 |
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| author | Karolina Żukowska Eva Pump Aleksandra E. Pazio Krzysztof Woźniak Luigi Cavallo Christian Slugovc |
| author_facet | Karolina Żukowska Eva Pump Aleksandra E. Pazio Krzysztof Woźniak Luigi Cavallo Christian Slugovc |
| author_sort | Karolina Żukowska |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-12-22T21:51:01Z |
| format | Article |
| id | doaj.art-7361f0345feb462d9b5b55a50d66664a |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-22T21:51:01Z |
| publishDate | 2015-08-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-7361f0345feb462d9b5b55a50d66664a2022-12-21T18:11:21ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972015-08-011111458146810.3762/bjoc.11.1581860-5397-11-158Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivityKarolina Żukowska0Eva Pump1Aleksandra E. Pazio2Krzysztof Woźniak3Luigi Cavallo4Christian Slugovc5Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa, PolandInstitute of Chemistry and Technology of Materials, Graz University of Technology, NAWI Graz, Stremayrgasse 9, 8010 Graz, AustriaBiological and Chemical Research Centre, Faculty of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089; Warszawa, PolandBiological and Chemical Research Centre, Faculty of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089; Warszawa, PolandKaust Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi ArabiaInstitute of Chemistry and Technology of Materials, Graz University of Technology, NAWI Graz, Stremayrgasse 9, 8010 Graz, AustriaTwo 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.https://doi.org/10.3762/bjoc.11.158DFT calculationsolefin metathesisring closing metathesisring-opening metathesis polymerisationruthenium |
| spellingShingle | Karolina Żukowska Eva Pump Aleksandra E. Pazio Krzysztof Woźniak Luigi Cavallo Christian Slugovc Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity Beilstein Journal of Organic Chemistry DFT calculations olefin metathesis ring closing metathesis ring-opening metathesis polymerisation ruthenium |
| title | Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity |
| title_full | Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity |
| title_fullStr | Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity |
| title_full_unstemmed | Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity |
| title_short | Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity |
| title_sort | consequences of the electronic tuning of latent ruthenium based olefin metathesis catalysts on their reactivity |
| topic | DFT calculations olefin metathesis ring closing metathesis ring-opening metathesis polymerisation ruthenium |
| url | https://doi.org/10.3762/bjoc.11.158 |
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