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Título : Acid−Base Reactions of Methylnickel Hydroxo, Alkoxo, and Amide Complexes with Carbon Acids. Studies on the Reactivity of Noncyclic Nickel Enolates
Autor : Cámpora, Juan, Matas, Inmaculada, Palma Ramírez, Pilar, Álvarez, Eleuterio, Graiff, Claudia, Tiripicchio, Antonio
Palabras clave : Hydroxo
Carbon acids
Enolate complex
Fecha de publicación : 27-Sep-2007
Editor: American Chemical Society
Resumen: Basic organonickel hydroxo, alkoxo, or amido complexes of composition Ni(Me)(X)(dippe) (X = OH, t-BuO, cyclo-NC4H8; dippe = i-Pr2PCH2CH2Pi-Pr2) react with enolizable ketones, esters, and nitriles, producing the corresponding enolate complexes. In the case of the hydroxo and alkoxo complexes, these reactions may lead to equilibrium mixtures, allowing a comparison of their respective basicities, while the amido compound reacts clean and quantitatively in all cases, allowing the isolation of the corresponding enolates. While the ketone derivatives display oxygen-bound enolate ligands, the ester and nitrile enolates bind the metal center through the carbon atom. The acetophenone enolate complex has strong nucleophilic properties and rapidly reacts with aldehydes (PhCHO) or CO2, affording the corresponding aldolate and carboxylate addition products.
Descripción : 10 páginas, 3 figuras, 2 tablas, 8 esquemas.
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ISSN: 0276-7333
DOI: 10.1021/om7007259
Citación : Organometallics 26(23): 5712-5721 (2007)
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