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  C−H Bond Activation of Benzene by Unsaturated η2-Cyclopropene and η2-Benzyne Complexes of Niobium

Boulho, C., Oulié, P., Vendier, L., Etienne, M., Pimienta, V., Locati, A., et al. (2010). C−H Bond Activation of Benzene by Unsaturated η2-Cyclopropene and η2-Benzyne Complexes of Niobium. Journal of the American Chemical Society, 132(40), 14239-14250. doi:10.1021/ja1061505.

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Boulho, Cédric1, 2, Autor
Oulié, Pascal1, 2, Autor
Vendier, Laure1, 2, Autor
Etienne, Michel1, 2, Autor
Pimienta, Véronique3, Autor
Locati, Abel4, Autor
Bessac, Fabienne4, Autor
Maseras, Feliu4, 5, Autor
Pantazis, Dimitrios A.6, Autor           
McGrady, John E.6, Autor
Affiliations:
1CNRS, Laboratoire de Chimie de Coordination (LCC), 205 Route de Narbonne, F-31077 Toulouse, France, ou_persistent22              
2Université de Toulouse, UPS, INPT, LCC, F-31077 Toulouse, France, ou_persistent22              
3Université de Toulouse, UPS, IMRCP, 118 Route de Narbonne, F-31062 Toulouse, France, ou_persistent22              
4Institute of Chemical Research of Catalonia (ICIQ), Avgda, Països Catalans 16, 43007 Tarragona, Spain, ou_persistent22              
5Unitat de Química Física, Edifici Cn, Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia, Spain, ou_persistent22              
6Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, United Kingdom, ou_persistent22              

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 Zusammenfassung: We report the synthesis of a niobium cyclopropyl complex, TpMe2NbMe(c-C3H5)(MeCCMe), and show that thermal loss of methane from this compound generates an intermediate that is capable of activating both aliphatic and aromatic C−H bonds. Isotopic labeling, trapping studies, a detailed kinetic analysis, and density functional theory all suggest that the active intermediate is an η2-cyclopropene complex formed via β-hydrogen abstraction rather than an isomeric cyclopropylidene species. C−H activation chemistry of this type represents a rather unusual reactivity pattern for η2-alkene complexes but is favored in this case by the strain in the C3 ring which prevents the decomposition of the key intermediate via loss of cyclopropene.

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Sprache(n): eng - English
 Datum: 2010-07-122010-09-212010-10-13
 Publikationsstatus: Erschienen
 Seiten: 12
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/ja1061505
 Art des Abschluß: -

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Titel: Journal of the American Chemical Society
  Andere : JACS
  Kurztitel : J. Am. Chem. Soc.
Genre der Quelle: Zeitschrift
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Ort, Verlag, Ausgabe: Washington, DC : American Chemical Society
Seiten: - Band / Heft: 132 (40) Artikelnummer: - Start- / Endseite: 14239 - 14250 Identifikator: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870