N, P, and As Ylides and Aza- and Arsa-Wittig Reactions from Topological Analyses of Electron Density
Impacto
Scholar |
Otros documentos de la autoría: Sánchez González, Ángel; Melchor, Santiago; Dobado Jiménez, José A.; Silvi, Bernard; Andres, Juan
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/10.1021/jp204441p |
Metadatos
Título
N, P, and As Ylides and Aza- and Arsa-Wittig Reactions from Topological Analyses of Electron DensityAutoría
Fecha de publicación
2011-07Editor
ACSISSN
1089-5639Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
http://pubs.acs.org/doi/full/10.1021/jp204441pVersión
info:eu-repo/semantics/publishedVersionResumen
The nature of bonding between N, P, and As constituent atoms in ylide systems with the R3XYR′ formula (X = N, P, As; Y = N, P, As; R = F, H; R′ = H, CH3) has been characterized by ab initio (MP2/6-311++G**) and density ... [+]
The nature of bonding between N, P, and As constituent atoms in ylide systems with the R3XYR′ formula (X = N, P, As; Y = N, P, As; R = F, H; R′ = H, CH3) has been characterized by ab initio (MP2/6-311++G**) and density functional theory (B3LYP/6-311++G**) calculations. Its electronic structure has been analyzed through electron density with the quantum theory of atoms in molecules and the electron localization function (ELF). The characteristics of the central bond are inspected with the calculated rotational barriers. The results show that N has a behavior different from that of the remaining pnicogen atoms (P, As), where the bond is much stronger. Fluorine substituents strengthen the X–Y bond, reduce the bond distance, and increase the electron density in the central bond so that the substituent pulls charge from the bond in the pnicogen X atom. For the N–pnicogen ylides, the results showed different bonding characters between F and X atoms; depending on the position of the F atom, the difference of the bond character is sensed by the basin synaptic order, as it is deduced from the analysis of the ELF basins. The energy profiles of the rotational barriers have been calculated at the MP2/6-311++G** level, indicating that the electronegativity of the substituents is a relevant factor that has consequences in the characteristics of the X–Y bond. [-]
Publicado en
Journal of Physical Chemistry A, 2011, 115 (29)Derechos de acceso
Copyright © 2011 American Chemical Society
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/restrictedAccess
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/restrictedAccess
Aparece en las colecciones
- QFA_Articles [811]