English   español  
Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/37007
logo share SHARE logo core CORE   Add this article to your Mendeley library MendeleyBASE

Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Exportar a otros formatos:


Cyclic Enolates of Ni and Pd: Equilibrium between C- and O-Bound Tautomers and Reactivity Studies

AuthorsCámpora, Juan ; Maya, Celia ; Palma, Pilar ; Carmona, Ernesto ; Gutiérrez-Puebla, Enrique ; Ruiz, Caridad; Graiff, Claudia; Tiripicchio, Antonio
KeywordsAldol reactions
O ligands
Issue Date21-Sep-2005
CitationChemistry - a European Journal 11(23): 6889- 6904 (2005)
Abstract2-Acylaryl complexes of Ni and Pd containing chelating diphosphines react with KtBuO to give metallacyclic enolate complexes. While coordination through the carbon atom is preferred in the case of Pd, the nickel O-enolate compounds are formed as the corresponding O-tautomers. Slow equilibration between O- and C-enolate tautomers is observed for the nickel complex with an unsubstituted enolate function (M-O-C=CH2). Theoretical DFT calculations suggest that the barrier for the tautomer exchange has its origin in the rigidity of the metallacycle. Whilst the C-enolate tautomer is unreactive towards aldehydes, the corresponding O-enolate adds to MeCHO and PhCHO, giving rise to products that retain the enolate functionality. The carbonylation of these products cleanly leads to the formation of enol lactones in a highly selective manner.
Description16 páginas, 3 figuras, 1 tabla, 13 esquemas.
Publisher version (URL)http://dx.doi.org/10.1002/chem.200500622
Appears in Collections:(IIQ) Artículos
(ICMM) Artículos
Files in This Item:
There are no files associated with this item.
Show full item record
Review this work

Related articles:

WARNING: Items in Digital.CSIC are protected by copyright, with all rights reserved, unless otherwise indicated.