DFT-Studies on Cobalt Catalyzed Cyclotrimerization Reactions. Mechanism and Origin of Reaction Improvement under Microwave Irradiation

A DFT computational mechanistic study of the [2+2+2] cyclotrimerization of a diyne with benzonitrile, catalyzed by a cobalt complex, has been carried out. Three alternative catalytic cycles have been examined together with the precatalytic step (responsible for the induction period). The favored mec...

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Detalles Bibliográficos
Autores: Rodríguez García, Antonio Manuel, Cebrián, Cristina, Prieto, Pilar, García, José Ignacio, Hoz Ayuso, Antonio de la, Díaz Ortiz, Ángel
Tipo de recurso: artículo
Fecha de publicación:2012
País:España
Institución:Universidad de Castilla-La Mancha
Repositorio:RUIdeRA. Repositorio Institucional de la UCLM
OAI Identifier:oai:ruidera.uclm.es:10578/38743
Acceso en línea:https://hdl.handle.net/10578/38743
Access Level:acceso abierto
Palabra clave:Spinstate changes
Cobalt
Cyclotrimerization
Density functional calculations
Microwave chemistry
Descripción
Sumario:A DFT computational mechanistic study of the [2+2+2] cyclotrimerization of a diyne with benzonitrile, catalyzed by a cobalt complex, has been carried out. Three alternative catalytic cycles have been examined together with the precatalytic step (responsible for the induction period). The favored mechanism takes place by means of an intramolecular metal-assisted [4+2] cycloaddition. The beneficial role of microwave activation has been studied. It is concluded that microwave irradiation can decrease the catalytic induction period through thermal effects and can also increase the triplet lifetime and promote the reaction, thus improving the final yield.