Artículo
Coupling of Aromatic Aldehydes with CO2Me-Substituted TpMe2Ir(III) Metallacyclopentadienes
Autor/es | Espinosa-Roa, Arián
Salazar Pereda, Verónica López Serrano, Joaquín Oñate Rodríguez, Enrique Alvarado Rodrı́guez, José G. Paneque Sosa, Margarita López Poveda, Manuel |
Departamento | Universidad de Sevilla. Departamento de Química Inorgánica |
Fecha de publicación | 2012 |
Fecha de depósito | 2018-10-02 |
Publicado en |
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Resumen | The fully CO2Me substituted aquo-iridacyclopentadiene 1 reacts with a variety of aromatic aldehydes, at 90–120 °C, with the formation of bicyclic Fischer-type carbenes, generated by the transfer of the aldehydic H atom to ... The fully CO2Me substituted aquo-iridacyclopentadiene 1 reacts with a variety of aromatic aldehydes, at 90–120 °C, with the formation of bicyclic Fischer-type carbenes, generated by the transfer of the aldehydic H atom to an α carbon of the metallacycle and concomitant bonding of the O atom to the adjacent β carbon. These carbenes have a thermodynamically favored anti configuration of these C–H and C–O bonds but it is proposed that an unobserved syn carbene is the kinetic primary product, which then easily epimerizes by adventitious water. Milder reaction conditions (25–60 °C) allow for the isolation of intermediate O-coordinated aldehyde adducts. While these reactions have been observed for a wide variety of aromatic aldehydes, 2-pyridinecarboxaldehyde behaves differently, as the reaction leads to a very stable N adduct, in spite of two isomeric O-bonded adducts being formed as kinetic products. |
Identificador del proyecto | CTQ2010-17476
CTQ2011-23459 Consolider-Ingenio 2010 CSD2007-00006 FQM-119 P09-FQM-4832 E35 025424 84453 |
Cita | Espinosa-Roa, A., Salazar Pereda, V., López Serrano, J., Oñate Rodríguez, E., Alvarado Rodrı́guez, J.G., Paneque Sosa, M. y López Poveda, M. (2012). Coupling of Aromatic Aldehydes with CO2Me-Substituted TpMe2Ir(III) Metallacyclopentadienes. Organometallics, 31 (8), 3185-3198. https://doi.org/10.1021/om3000554. |
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