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Estudio de la Influencia de la polarizabilidad del grupo vecino C=X, en la cinética de eliminación de cloruro de hidrógeno a partir de cloruros de alquilos β- sustituidos (X = CH2 , S, NH, PH), usando la teoría del funcional de la densidad
dc.contributor.author | Márquez Brazón, E. A. | spa |
dc.contributor.author | Flores-Sumoza, M. C. | spa |
dc.contributor.author | Cortes Gómez, E. | spa |
dc.contributor.author | Puello-Polo, E. | spa |
dc.date.accessioned | 2021-01-15T01:22:56Z | |
dc.date.available | 2021-01-15T01:22:56Z | |
dc.date.issued | 2018 | |
dc.identifier.issn | 0001-9704 | spa |
dc.identifier.uri | https://hdl.handle.net/11323/7688 | spa |
dc.description.abstract | The elimination kinetics of the compounds 5-chloro 2-methylpentene, 5-chloropentan-2-imine, (5-chloropentan-2-ylidene) phosphine and 5-chloropenta2-thione compounds were studied using the electron structure methods: B3LYP, MW1PW91 and PBEPBE with the basis set 6-31++G(2d,p), respectively, belonging to the computational package G09W. According to the elimination products, two possible reaction mechanisms were proposed: a discrete path through a four-member transition state and a intime ion-par via a 5-membered cyclic transition state, where the C = X group assists, anchimerically, the HCl elimination. With the exception of the group X = CH2, the favorable mechanism occurs through an intimate Ion-Pair type 5-membered TS, where the breaking of the C2 - Cl1 bond is the determining step of the reaction. The concept of stabilization energy by anchimeric assistance was proposed and used to determine the following order of reactivity: S> PH> NH> O; A linear relationship between the free activation energy and the molecular polarizability of the transition states was found, suggesting that this parameter plays a pivotal role in the anchimerical assistance observed in these systems. | spa |
dc.description.abstract | La cinética de eliminación de los compuestos 5-cloro-2-metilpenteno, 5-cloropentan-2-imina, (5-cloropentan-2-iliden) fosfina y 5-cloropenta-2-tiona fue estudiada usando los métodos de estructura electrónica: B3LYP, MW1PW91 y PBEPBE con el set de bases 6-31++G(2d,p), pertenecientes al paquete computacional G09W. De acuerdo a los productos de eliminación, dos posibles mecanismos de reacción fueron propuestos: una vía discreta, a través de un estado de transición de cuatro miembros y una vía ión par-íntimo, vía un estado de transición cíclico de 5 miembros donde el grupo C=X asiste, anquiméricamente, la salida del átomo de cloro. Con la excepción del grupo X=CH2, el mecanismo favorable resulto ser el que ocurre a través de un TS de 5 miembros tipo Ion-Par íntimo, donde la ruptura del enlace C2 -Cl1 es el paso determinante de la reacción. El concepto de energía de estabilización por asistencia anquimérica fue propuesto y usado para determinar el siguiente orden de reactividad: S>PH>NH>O. Se encontró una relación lineal entre la energía libre de activación y la polarizabilidad molecular de los estados de transición, sugiriendo que este parámetro juega un rol fundamental en la asistencia anquimérica observada en estos sistemas. | spa |
dc.format.mimetype | application/pdf | spa |
dc.language.iso | spa | |
dc.publisher | Corporación Universidad de la Costa | spa |
dc.rights | Attribution-NonCommercial-ShareAlike 4.0 International | spa |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-sa/4.0/ | spa |
dc.source | Afinidad: Revista de química teórica y aplicada | spa |
dc.subject | Asistencia anquimérica | spa |
dc.subject | energía de estabilización | spa |
dc.subject | estado de transición | spa |
dc.subject | energía libre de activación | spa |
dc.subject | DFT | spa |
dc.subject | Ion-Par íntimo | spa |
dc.subject | Anchimeric Assitance | spa |
dc.subject | Activation free energy | spa |
dc.subject | DFT | spa |
dc.subject | intimate Ion-Par | spa |
dc.subject | stabilization energy | spa |
dc.subject | Transition state | spa |
dc.title | Estudio de la Influencia de la polarizabilidad del grupo vecino C=X, en la cinética de eliminación de cloruro de hidrógeno a partir de cloruros de alquilos β- sustituidos (X = CH2 , S, NH, PH), usando la teoría del funcional de la densidad | spa |
dc.type | Artículo de revista | spa |
dc.rights.accessrights | info:eu-repo/semantics/openAccess | spa |
dc.identifier.instname | Corporación Universidad de la Costa | spa |
dc.identifier.reponame | REDICUC - Repositorio CUC | spa |
dc.identifier.repourl | https://repositorio.cuc.edu.co/ | spa |
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dc.title.translated | Study of the Influence of the polarization of the neighboring group C = X, in the kinetics of hydrogen chloride removal from b- (substituted) alkyl chlorides (X = CH2 , S, NH, PH), using the density functional theory | spa |
dc.type.coar | http://purl.org/coar/resource_type/c_6501 | spa |
dc.type.content | Text | spa |
dc.type.driver | info:eu-repo/semantics/article | spa |
dc.type.redcol | http://purl.org/redcol/resource_type/ART | spa |
dc.type.version | info:eu-repo/semantics/acceptedVersion | spa |
dc.type.coarversion | http://purl.org/coar/version/c_ab4af688f83e57aa | spa |
dc.rights.coar | http://purl.org/coar/access_right/c_abf2 | spa |
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