Theoretical study of the reactions of the hydroselenyl radical (HSe●) with the selenenic radical (HSeO●)

Dublin Core

Título

Theoretical study of the reactions of the hydroselenyl radical (HSe●) with the selenenic radical (HSeO●)

Tema

SELENIO
AZUFRE
RADICALES
BIBLIOGRAFIA NACIONAL QUIMICA
2018

Abstract

The formation of selenium species in some biological processes involves the generation of ionic and radical intermediates such as RSe●, RSe−, RSeO●, and RSeO−, among others. We performed a theoretical study of the possible mechanisms for the reaction of the two simplest Se radicals—the hydroselenyl (HSe●) and selenenic (HSeO●) radicals, in which the possible products, intermediates, and transition-state structures were investigated. Density functional theory (DFT) was applied at the B3LYP/6–311++G(3df,3pd) level and the Ahlrichs Coulomb fitting basis sets were employed with an effective core potential (ECP) for both Se atoms. The same procedure was used to calculate the electronic density. All calculations were also performed using the M06-2X functional, which describes weaker bonds better than B3LYP does. In the reaction of interest, the so-called CR complex (HSe····SeOH) is formed initially. After passing through the transition state TS1, cis-HSeSeOH is obtained as a product. If a low barrier is then overcome (passing through the transition state TS32), the trans-HSeSeOH species is obtained. The CR complex can also rearrange into the intermediate INT after overcoming the barrier presented by the transition state TS2. Additionally, the decomposition of INT to H2O and 1Se2 is possible through another transition state. This reaction is not included in this study. We also observed a second possible route for the conversion of INT to one of the HSeSeOH species; this route occurs through two pathways (with transition states TS31 and TS32). A comparison of some of the results with those obtained for sulfur analogs along the same pathways is also presented in this work.

Autor

Vega Teijido, Mauricio Angel
Kieninger, Martina

Fuente

Journal of Molecular Modeling v. 24, no. 1, 2018. --p. 1-8 .--e3

Editor

Springer

Fecha

2018

Derechos

Información sobre Derechos de Autor (Por favor lea este aviso antes de abrir los documentos u objetos) La legislación uruguaya protege el derecho de autor sobre toda creación literaria, científica o artística, tanto en lo que tiene que ver con sus derechos morales, como en lo referente a los derechos patrimoniales con sujeción a lo establecido por el derecho común y las siguientes leyes (LEY 9.739 DE 17 DE DICIEMBRE DE 1937 SOBRE PROPIEDAD LITERARIA Y ARTISTICA CON LAS MODIFICACIONES INTRODUCIDAS POR LA LEY DE DERECHO DE AUTOR Y DERECHOS CONEXOS No. 17.616 DE 10 DE ENERO DE 2003, LEY 17.805 DE 26 DE AGOSTO DE 2004, LEY 18.046 DE 24 DE OCTUBRE DE 2006) ADVERTENCIA - La consulta de este documento queda condicionada a la aceptación de las siguientes condiciones de uso: Este documento es únicamente para usos privados enmarcados en actividades de investigación y docencia. No se autoriza su reproducción con fines de lucro. Esta reserva de derechos afecta tanto los datos del documento como a sus contenidos. En la utilización o cita de partes debe indicarse el nombre de la persona autora.

Formato

PDF

Idioma

Inglés

Tipo

Artículo

Identificador

DOI: 10.1007/s00894-017-3535-1

Document Item Type Metadata

Original Format

PDF
Fecha de agregación
March 26, 2019
Colección
Bibliografía Nacional Química
Tipo de Elemento
Document
Etiquetas
, ,
Citación
Vega Teijido, Mauricio Angel, “Theoretical study of the reactions of the hydroselenyl radical (HSe●) with the selenenic radical (HSeO●),” RIQUIM - Repositorio Institucional de la Facultad de Química - UdelaR, accessed December 8, 2019, http://riquim.fq.edu.uy/items/show/5655.
Archivos