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Título: | Generation of Metallacyclic Structures from the Reactions of Vinyl Ethers with a TpMe2IrIII Compound |
Autor: | Paneque, Margarita CSIC ORCID; López Poveda, Manuel; López Santos, Laura; Carmona, Ernesto CSIC ORCID; Mereiter, Kurt | Palabras clave: | Vinyl ethers Metallacycle structures X-ray crystallography Alkyl Alkoxides Carbene Iridacyclopentenes Hydrocarbyl ligand |
Fecha de publicación: | 30-oct-2008 | Editor: | American Chemical Society | Citación: | Organometallics 27(23): 6353-6359 (2008) | Resumen: | The vinyl ethers CH2 CHOEt and CH2 CHOPrn react with the IrIII fragment [TpMe2Ir(C6H5)2] [1; TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate] with the formation of unusual metallacyclic structures. Each of the ethers gives rise to three different metallacyclic units in complexes 2−4. Compounds 2are iridacyclopentenes that contain a chelating organic ligand with alkyl and carbene termini, {I r[ C(OR)CH2CH(OR) CH2]} (R = Et, Prn), resulting from the C−C coupling of two molecules of the ether, following prior vinylic C−H activation in one of them. They readily eliminate a molecule of the respective alcohol, ROH, in an acid-catalyzed process that leads to metallacyclopenta-1,3-diene units in 4 {I r[ C(OR)CH CH CH2]}. Complexes 3 have a more complex metallacyclic structure resulting from tridentate coordination of a formally dianionic ligand that possesses alkyl, alkoxide, and carbene functionalities. Generation of this ligand involves the participation of two molecules of the vinyl ether, with one of them undergoing Cvinyl−O bond cleavage. The metallacyclic units that define the molecular structures of 2−4 have been unequivocally characterized by X-ray crystallography. | Descripción: | 7 páginas, 3 figuras, 1 tabla, 3 esquemas. | Versión del editor: | http://dx.doi.org/10.1021/om800844x | URI: | http://hdl.handle.net/10261/37720 | DOI: | 10.1021/om800844x | ISSN: | 0276-7333 |
Aparece en las colecciones: | (IIQ) Artículos |
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