Mechanism of the Ru-Allenylidene to Ru-Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis
The intramolecular allenylidene RuCl2(PR3)2(C=C=CPh2) to indenylidene RuCl2(PR3)2(Ind) rearrangement that occurs during the synthesis of Ru-based precatalysts for olefin metathesis is presented. In the absence of acid, the ring closure via C-H activation was shown to be unfavored for energy barriers...
| 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:10256/13298 |
| Acceso en línea: | http://hdl.handle.net/10256/13298 |
| Access Level: | acceso embargado |
| Palabra clave: | Metàtesi (Química) Metathesis (Chemistry) Alquens Alkenes |
| Sumario: | The intramolecular allenylidene RuCl2(PR3)2(C=C=CPh2) to indenylidene RuCl2(PR3)2(Ind) rearrangement that occurs during the synthesis of Ru-based precatalysts for olefin metathesis is presented. In the absence of acid, the ring closure via C-H activation was shown to be unfavored for energy barriers up to 70 kcal/mol. Thus, it turned out to be HCl (or other acid) that plays a crucial role during formation of the indenylidene, as the upper energy barrier decreases to a reasonable 35 kcal/mol. Moreover, we proved computationally that depending on the nature of the phosphine the intramolecular rearrangement is either facilitated (PPh3) or slightly hampered (PCy3), which is in line with experimental results |
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