The Role of Solvent on the Mechanism of Proton Transfer to Hydride Complexes: The Case of the [W3PdS4H3(dmpe)3(CO)]+ Cubane Cluster
Impacto
Scholar |
Otros documentos de la autoría: Algarra, Andrés G.; García Basallote, Manuel; Feliz Rodríguez, Marta; Fernández-Trujillo, M. Jesús; Llusar, Rosa; Safont Villarreal, Vicent Sixte
Metadatos
Mostrar el registro completo del ítemcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
comunitat-uji-handle4:
INVESTIGACIONEste recurso está restringido
http://dx.doi.org/10.1002/chem.200902233 |
Metadatos
Título
The Role of Solvent on the Mechanism of Proton Transfer to Hydride Complexes: The Case of the [W3PdS4H3(dmpe)3(CO)]+ Cubane ClusterAutoría
Fecha de publicación
2010Editor
Wiley-VCHISSN
0947-6539Cita bibliográfica
Chemistry - A European Journal (2010), 16, 5, p. 1613–1623Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
http://onlinelibrary.wiley.com/doi/10.1002/chem.200902233/abstractVersión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
The kinetics of reaction of the [W3PdS4H3(dmpe)3(CO)]+ hydride cluster (1+) with HCl has been measured in dichloromethane, and a second-order dependence with respect to the acid is found for the initial step. In the ... [+]
The kinetics of reaction of the [W3PdS4H3(dmpe)3(CO)]+ hydride cluster (1+) with HCl has been measured in dichloromethane, and a second-order dependence with respect to the acid is found for the initial step. In the presence of added BF4− the second-order dependence is maintained, but there is a deceleration that becomes more evident as the acid concentration increases. DFT calculations indicate that these results can be rationalized on the basis of the mechanism previously proposed for the same reaction of the closely related [W3S4H3(dmpe)3]+ cluster, which involves parallel first- and second-order pathways in which the coordinated hydride interacts with one and two acid molecules, and ion pairing to BF4− hinders formation of dihydrogen bonded adducts able to evolve to the products of proton transfer. Additional DFT calculations are reported to understand the behavior of the cluster in neat acetonitrile and acetonitrile–water mixtures. The interaction of the HCl molecule with CH3CN is stronger than the WH⋅⋅⋅HCl dihydrogen bond and so the reaction pathways operating in dichloromethane become inefficient, in agreement with the lack of reaction between 1+ and HCl in neat acetonitrile. However, the attacking species in acetonitrile–water mixtures is the solvated proton, and DFT calculations indicate that the reaction can then go through pathways involving solvent attack to the W centers, while still maintaining the coordinated hydride, which is made possible by the capability of the cluster to undergo structural changes in its core. [-]
Derechos de acceso
Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/closedAccess
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/closedAccess
Aparece en las colecciones
- QFA_Articles [818]