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

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Abstract

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 π-system to the nitronium ion prior to σ-complex formation. The formation of an initial π-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.

Gibbs free energy diagram for phenol nitration in the gas phase at a temperature of 298.15K calculated at the G3(MP2)//B3-CEP level of theory.

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Acknowledgments

We acknowledge financial support from FAPESP (Fundação de Amparo à Pesquisa do Estado de São Paulo—Center for Computational Engineering and Sciences, grant 2013/08293-7), CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico), and FAEPEX-UNICAMP (Fundo de Apoio ao Ensino, à Pesquisa e à Extensão da UNICAMP). The National Center of High Performance Computing in São Paulo (CENAPAD–SP) is acknowledged for making its computational facilities available to us.

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  1. Carlos Murilo Romero Rocha

    Present address: Departamento de Química, Universidade de Coimbra, 3004-535, Coimbra, Portugal

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  1. Instituto de Química, Universidade Estadual de Campinas, Barão Geraldo, 13083-970, Campinas, São Paulo, Brazil, P.O. Box 6154

    Carlos Murilo Romero Rocha, José Augusto Rosário Rodrigues, Paulo José Samenho Moran & Rogério Custodio

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  1. Carlos Murilo Romero Rocha
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  2. José Augusto Rosário Rodrigues
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Correspondence to Rogério Custodio.

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ESM 1

G3(MP2)//B3-CEP molecular energies, thermal corrections to 298.15 K, and geometric parameters for the optimized structures calculated at B3LYP/CEP-P31G(d) level. For transition structures in which imaginary frequencies were observed, displacement vectors of the imaginary normal modes are shown. (DOCX 322 kb)

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Rocha, C.M.R., Rodrigues, J.A.R., Moran, P.J.S. et al. An interpretation of the phenol nitration mechanism in the gas phase using G3(MP2)//B3-CEP theory. J Mol Model 20, 2524 (2014). https://doi.org/10.1007/s00894-014-2524-x

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