Gas-phase Activation of Methane with PtOH+

Publication date: Available online 9 November 2018Source: Computational and Theoretical ChemistryAuthor(s): Shaoli Liu, Jianbo Cheng, Qingzhong Li, Wenzuo LiAbstractBased on the density functional theory (DFT) level, the thermal reaction of PtOH+ with methane has been investigated theoretically using the empirically parametrized hybrid functional B3LYP. The favorable path for the reaction of PtOH+ + CH4 is the channel of the elimination of H2O. The overall reaction is exothermic by 16.5 kcal/mol. The NBO analysis demonstrated that the ligand effect resulting in the electronic occupies in the quasi-restricted orbitals and also shows a proton-coupled electron transfer component in 3TS2-H2O. By comparing among the reactions of Pt+, [Pt(H)(OH)]+ and PtOH+ with CH4, PtOH+ is more reactive to methane than Pt+ and [Pt(H)(OH)]+ thermodynamically. These results can not only deepen the understanding of the mechanism, but also guide the reasonable design of catalysts.Graphical abstractQuasi-restricted orbital diagrams for the transition state after 3PtHOH(CH3)+

Source: Computational and Theoretical Chemistry - November 9, 2018 Category: Chemistry Source Type: research