Acid−Base Reactions of Methylnickel Hydroxo, Alkoxo, and Amide Complexes with Carbon Acids. Studies on the Reactivity of Noncyclic Nickel Enolates

descriptionPublicationkeyboard_double_arrow_right Article 27 Sep 2007 Italy English Publisher:American Chemical Society (ACS)Journal:Organometallics, volume 26, pages 5,712-5,721 (issn: 0276-7333, eissn: 1520-6041,

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Authors: CAMPORA J.; MATAS I.; PALMA P.; ALVAREZ E.; GRAIFF, Claudia; TIRIPICCHIO, Antonio;

doi: 10.1021/om7007259

handle: 10261/37727 , 11381/1653638

Acid−Base Reactions of Methylnickel Hydroxo, Alkoxo, and Amide Complexes with Carbon Acids. Studies on the Reactivity of Noncyclic Nickel Enolates

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Abstract

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.

Financial support from the DGI (Project CTQ2006-05527/BQU) and Junta de Andalucía (Project P06-FQM-01704) is gratefully acknowledged. I.M. is thankful for a research fellowship from the Consejo Superior de Investigaciones Científicas (I3P program).

10 páginas, 3 figuras, 2 tablas, 8 esquemas.

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Country

Italy

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Keywords

Temperatures, Carbon acids, Organonickel, Reactivity, Alkoxo, Amido, 540, Hydroxo, Enolate complex

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