C-C Bond Activation of the NHC Ligand of an Osmium-Amido Complex

Bolaño, T. ; Buil, M. L. (Universidad de Zaragoza) ; Esteruelas, M. A. (Universidad de Zaragoza) ; Izquierdo, S. ; Lalrempuia, R. ; Oliván, M. ; Oñate, E.

Resumen: Treatment of (η6-p-cymene)OsCl2(IPr) (1, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene) with AgBF4 in acetonitrile leads to [(η6-p-cymene)Os(CH3CN)2(IPr)][BF4]2 (2), which reacts with aniline and cyclohexylamine to afford [(η6-p-cymene)Os(═NHR)(IPr)]BF4 (R = Ph (3), Cy (4)). Complexes 3 and 4 have also been prepared by addition of nBuLi to tetrahydrofuran solutions of the amine compounds [(η6-p-cymene)OsCl(NH2R)(IPr)]BF4 (R = Ph (6), Cy (7)). Complex 4 decomposes in tetrahydrofuran at 100 °C and in the presence of H2O to give cyclohexanone, propane, and [η6-p-cymene)tiebar above startOs{tiebar below startCCHCHCHC(iPr)tiebar below endCtiebar below startNCHCHN(C6H3iPr2)tiebar below endtiebar above endC}(NH3)]BF4 (8). In dichloromethane at 50 °C, 4 evolves to [(η6-p-cymene)OsH(NH═tiebar above startCCH2CH2CH2CH2tiebar above endCH2)(IPr)]BF4 (9), which also gives 8 in tetrahydrofuran at 100 °C and in the presence of H2O. On the basis of these transformations, a mechanism for the formation of 8 is proposed.

Idioma: Inglés

DOI: 10.1021/om100684a

Año: 2010

Publicado en: Organometallics 29, 20 (2010), 4517-4523
ISSN: 0276-7333

Factor impacto JCR: 3.888 (2010)

Categ. JCR: CHEMISTRY, ORGANIC rank: 10 / 56 = 0.179 (2010) - Q1 - T1
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 6 / 43 = 0.14 (2010) - Q1 - T1

Financiación: info:eu-repo/grantAgreement/ES/DGA/E35
Financiación: info:eu-repo/grantAgreement/ES/MICINN/CSD2007-00006
Financiación: info:eu-repo/grantAgreement/ES/MICINN/CTQ2008-00810

Tipo y forma: Article (PostPrint)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)