Mechanism of CO2 Fixation by IrI–X Bonds (X = OH, OR, N, C)
KGaA, Weinheim.Density functional theory calculations have been used to investigate the CO2 fixation mechanism proposed by Nolan et al. for the IrI complex [Ir(cod)(IiPr)(OH)] (1; cod = 1,5-cyclooctadiene; IiPr = 1,3-diisopropylimidazol-2-ylidene) and its derivatives. For 1, our results suggest that...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2015 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:10256/13296 |
| Acceso en línea: | http://hdl.handle.net/10256/13296 |
| Access Level: | acceso embargado |
| Palabra clave: | Funcional de densitat, Teoria del Density functionals Química verda Green chemistry Catàlisi homogènia Homogeneous catalysis |
| Sumario: | KGaA, Weinheim.Density functional theory calculations have been used to investigate the CO2 fixation mechanism proposed by Nolan et al. for the IrI complex [Ir(cod)(IiPr)(OH)] (1; cod = 1,5-cyclooctadiene; IiPr = 1,3-diisopropylimidazol-2-ylidene) and its derivatives. For 1, our results suggest that CO2 insertion is the rate-limiting step rather than the dimerization step. Additionally, in agreement with the experimental results, our results show that CO2 insertion into the Ir-OR1 (R1 = H, methyl, and phenyl) and Ir-N bonds is kinetically facile, and the calculated activation energies span a range of only 12.0-23.0 kcal/mol. Substantially higher values (35.0-50.0 kcal/mol) are reported for analogous Ir-C bonds |
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