C-H Bond Activation of Benzene by Unsaturated η-Cyclopropene and η-Benzyne Complexes of Niobium.
We report the synthesis of a niobium cyclopropyl complex, TpNbMe(c-CH)(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, an...
| Published in: | Journal of the American Chemical Society Vol. 132; no. 40; pp. 14239 - 14251 |
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| Main Authors: | , , , , , , , , , |
| Format: | Article |
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American Chemical Society
10/13/2010
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=54626918&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 54626918 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 10/13/2010 vid: 132 iid: 40 pid: 997 pub: American Chemical Society artinfo: ui: 54626918 10.1021/ja1061505 ppf: 14239 ppct: 12 formats: tig: atl: C-H Bond Activation of Benzene by Unsaturated η-Cyclopropene and η-Benzyne Complexes of Niobium. aug: au: Boulho, Cédric Oulié, Pascal Vendier, Laure Etienne, Michel Pimienta, Véronique Locati, Abel Bessac, Fabienne Maseras, Feliu Pantazis, Dimitrios A. McGrady, John E. affil: CNRS, Laboratoire de Chimie de Coordination (LCC), 205 Route de Narbonne, F-31077 Toulouse, France Université de Toulouse, UPS, INPT, LCC, F-31077 Toulouse France, Université de Toulouse, UPS, IMRCP, 118 Route de Narbonne, F-31062 Toulouse, France Institute of Chemical Research of Catalonia (1CIQ), Avgda. Palsos Catalans 16, 43007 Tarragona, Spain Unitat de Quimica Fisica, Edition, Universitat Autonoma de Barcelona, 08193 Bellaterra, Catalonia, Spain Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford South Parks Road, Oxford OXI 3QR, United Kingdom su: Complex compounds synthesis Niobium Benzene Density functionals Hydrogen spectra Reactivity (Chemistry) sug: subj: Complex compounds synthesis Niobium Benzene Density functionals Hydrogen spectra Reactivity (Chemistry) ab: We report the synthesis of a niobium cyclopropyl complex, TpNbMe(c-CH)(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 η-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 η-alkene complexes but is favored in this case by the strain in the C ring which prevents the decomposition of the key intermediate via loss of cyclopropene. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
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