Selective hydration of nitriles to amides promoted by an Os-NHC catalyst: Formation and X-ray characterization of k2-amidate intermediates

Buil, M. L. (Universidad de Zaragoza) ; Cadierno, V. ; Esteruelas, M. A. (Universidad de Zaragoza) ; Gimeno, J. ; Herrero, J. ; Izquierdo, S. (Universidad de Zaragoza) ; Oñate, E.

Resumen: The complex [Os(η6-p-cymene)(OH)IPr]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CF3SO3) reacts with benzonitrile and acetonitrile to afford the κ2-amidate derivatives [Os(η6-p-cymene){κ2O,N-NHC(O)R}IPr]OTf (R = Ph (2), CH3 (3)). Their formation has been investigated by DFT calculations (B3PWP1), starting from the model intermediate [Os(η6-benzene)(OH)(CH3CN)IMe]+ (IMe = 1,3-bis(2,6-dimethylphenyl)imidazolylidene). Complex 2 has been characterized by X-ray diffraction analysis. In the presence of water, the κ2-amidate species release the corresponding amides and regenerate 1. In agreement with this, complex 1 has been found to be an efficient catalyst for the selective hydration of a wide range of aromatic and aliphatic nitriles to amides, including substituted benzonitriles, cyanopyridines, acetonitrile, and 2-(4-isobutylphenyl)propionitrile among others. The mechanism of the catalysis is also discussed.

Idioma: Inglés

DOI: 10.1021/om3006799

Año: 2012

Publicado en: Organometallics 31, 19 (2012), 6861-6867
ISSN: 0276-7333

Factor impacto JCR: 4.145 (2012)

Categ. JCR: CHEMISTRY, ORGANIC rank: 11 / 57 = 0.193 (2012) - Q1 - T1
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 6 / 44 = 0.136 (2012) - 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/CTQ2010-14796
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2011-23459

Tipo y forma: Article (Published version)

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