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Investigations on the Coupling of Ethylene and Alkynes in Tp Me2 Ir Compounds: Water as an Effective Trapping Agent

Opened Access Investigations on the Coupling of Ethylene and Alkynes in Tp Me2 Ir Compounds: Water as an Effective Trapping Agent

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Autor: Álvarez González, Eleuterio
Paneque Sosa, Margarita
Martín Posadas, Cristina Isabel
López Poveda, Manuel
Rendón Márquez, Nuria
Mereiter, Kurt
Departamento: Universidad de Sevilla. Departamento de Química Inorgánica
Fecha: 2007
Tipo de documento: Artículo
Resumen: The reaction of the bis(ethylene) complex [TpMe2Ir(C2H4)2] (1) (TpMe: hydrotris(3,5-dimethylpyrazolyl)borate) with two equivalents of dimethyl acetylenedicarboxylate (DMAD) in CH2Cl2 at 25 °C gives the hydride–alkenyl species [TpMe2IrH{C(R)=C(R)C(R)=C(R)CH=CH2}] (2, R: CO2Me) in high yield. A careful study of this system has established the active role of a number of intermediates en route to producing 2. The first of these is the iridium(I) complex [TpMe2Ir(C2H4)(DMAD)] (4) formed by substitution of one of the ethylene ligands in 1 by a molecule of DMAD. Complex 4 reacts further with another equivalent of the alkyne to give the unsaturated metallacyclopentadiene [TpMe2Ir{C(R)=C(R)C(R)=C(R)}], which can be trapped by added water to give adduct 7, or can react with the C2H4 present in solution generating complex 2. This last step has been shown to proceed by insertion of ethylene into one of the Ir-C bonds of the metallacyclopentadiene and subsequent β-H elimination. Complex 1 reacts s...
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Tamaño: 401.7Kb
Formato: PDF

URI: https://hdl.handle.net/11441/70956

DOI: 10.1002/chem.200601500

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