title: C-H bond activation of methane in aqueous solution: a hybrid quantum mechanical/effective fragment potential study.
abstract: In this study, we investigated the C-H bond activation of methane catalyzed by the complex [PtCl(4)](2-), using the hybrid quantum mechanical/effective fragment potential (EFP) approach. We analyzed the structures, energetic properties, and reaction mechanism involved in the elementary steps that compose the catalytic cycle of the Shilov reaction. Our B3LYP/SBKJC/cc-pVDZ/EFP results show that the methane activation may proceed through two pathways: (i) electrophilic addition or (ii) direct oxidative addition of the C-H bond of the alkane. The electrophilic addition pathway proceeds in two steps with formation of a σ-methane complex, with a Gibbs free energy barrier of 24.6 kcal mol(-1), followed by the cleavage of the C-H bond, with an energy barrier of 4.3 kcal mol(-1) . The activation Gibbs free energy, calculated for the methane uptake step was 24.6 kcal mol(-1), which is in good agreement with experimental value of 23.1 kcal mol(-1) obtained for a related system. The results shows that the activation of the C-H bond promoted by the [PtCl(4)](2-) catalyst in aqueous solution occurs through a direct oxidative addition of the C-H bond, in a single step, with an activation free energy of 25.2 kcal mol(-1), as the electrophilic addition pathway leads to the formation of a σ-methane intermediate that rapidly undergoes decomposition. The inclusion of long-range solvent effects with polarizable continuum model does not change the activation energies computed at the B3LYP/SBKJC/cc-pVDZ/EFP level of theory significantly, indicating that the large EFP water cluster used, obtained from Monte Carlo simulations and analysis of the center-of-mass radial pair distribution function, captures the most important solvent effects.
authors.affiliation: Laboratório de Química Computacional e Modelagem Molecular (LQC-MM), Departamento de Química, ICEx, Universidade Federal de Minas Gerais, Campus Universitário Pampulha, 31270-901 Belo Horizonte, Minas Gerias, Brazil.
authors.forename: Júlio C S
authors.initials: JC
authors.lastname: Da Silva
authors.forename: Willian R
authors.initials: WR
authors.lastname: Rocha
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D008697:Methane / Q000737:chemistry*; D009944:Organoplatinum Compounds / Q000737:chemistry; D011789:Quantum Theory; D012996:Solutions; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D000438:Alcohols; D009944:Organoplatinum Compounds; D012996:Solutions; D014867:Water; D008697:Methane