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Título: | NH-tautomerization of 2-substituted pyridines and quinolines on osmium and ruthenium: Determining factors and mechanism |
Autor: | Esteruelas, Miguel A. CSIC ORCID; Fernández-Álvarez, Francisco J. CSIC ORCID; Oñate, Enrique CSIC ORCID | Fecha de publicación: | 2008 | Editor: | American Chemical Society | Citación: | Organometallics 27(23): 6236-6244 (2008) | Resumen: | Complexes MH2Cl2(PiPr3) 2 (M = Os (1), Ru (1a)) promote the NH-tautomerization of 2-methylpyridine and stabilize the resulting NH-tautomer to afford the dihydrogen derivatives MCl2(η2-H2) {κ-C[HNC5H3Me] }(PiPr3) 2 (M = Os (2), Ru (3)), containing the heterocycle coordinated by the Cα atom. In dichloromethane under reflux, complex 3 loses the coordinated hydrogen molecule to give the five-coordinate derivative RuCl 2{κ-C-[HNC5H3Me])(PPr3) 2 (4). In contrast to 2-methylpyridine, the reactions of 1 and la with pyridine lead to MCl2(κ-N-[NC5H 5]})3(PiPr3) (M = Os (5), Ru (5a)), containing the heterocycle coordinated by the lone pair of the nitrogen. DFT calculations using PMe3 as a model of PPr3 show that the formation of 2 and the related quinoline complex OsCl2(η 2-H2){κ-C-[HNC9H6]}(P iPr3)2 (6) involves an intermolecular osmium to nitrogen hydrogen migration, the subsequent Cα-H bond activation of the protonated heterocycle, and the dihydride-dihydrogen tautomerization of the resulting dihydride. The structures of 2 and 5 have been determined by X-ray diffraction analysis. © 2008 American Chemical Society. | URI: | http://hdl.handle.net/10261/64865 | DOI: | 10.1021/om8007772 | Identificadores: | doi: 10.1021/om8007772 issn: 0276-7333 e-issn: 1520-6041 |
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