An interpretation of the phenol nitration mechanism in the gas phase using G3(MP2)//B3-CEP theory

Autor(es)

Romero Rocha, Carlos Murilo ^[1] ; Rosario Rodrigues, Jose Augusto ^[1] ; Samenho Moran, Paulo Jose ^[1] ; Custodio, Rogerio ^[1]

Afiliação do(s) autor(es)

^[1] Univ Estadual Campinas, Inst Quim, BR-13083970 Sao Paulo - Brazil

• Tipo de documento: Artigo Científico
• Fonte: Journal of Molecular Modeling; v. 20, n. 12 DEC 2014.
• Citações Web of Science: 4

Resumo

G3(MP2)//B3-CEP theory was applied to study the mechanism of phenol nitration in the gas phase, as promoted by the electrophile NO2+. The results of studying this mechanism at the G3(MP2)//B3-CEP level pointed to the occurrence of a single-electron transfer (SET) from the aromatic pi-system to the nitronium ion prior to sigma-complex formation. The formation of an initial pi-complex between the nitronium ion and phenol was not observed. Excellent agreement between the activation barriers predicted by G3(MP2)//B3-CEP and those yielded by other, more accurate, versions of the G3 theory showed that the former is a useful tool for studying reaction mechanisms, as G3(MP2)//B3-CEP is much less computationally expensive than other high-level methods. (AU)

• Processo FAPESP: 13/08293-7 - CECC - Centro de Engenharia e Ciências Computacionais
• Beneficiário: Munir Salomao Skaf
• Modalidade de apoio: Auxílio à Pesquisa - Centros de Pesquisa, Inovação e Difusão - CEPIDs