Density functional studies of thermal activation of methane by gas-phase [Pt(H)(OH)]+

The dehydrogenation reaction of [Pt(H)(OH)]+ toward methane has been investigated theoretically in this work. The mechanism of methane catalyzed by gas-phase ligated transition-metal [Pt(H)(OH)]+ have been carried out at the DFT (B3LYP) level based on the RECP + 6-311+g** basis set. Both doublet and quartet states potential energy surfaces for the reaction of [ Pt ( H ) ( OH ) ] + + CH 4 → [ Pt ( OH ) ( CH 3 ) ] + + H 2 were built up. Our calculations indicate that this reaction occurs as a kinetically efficient process on the doublet ground potential energy surface. The overall reaction in the favored doublet state is endothermic by 3.0 kcal/mol. [Pt(H)(OH)]+ is less reactive than Pt+ to the activation of methane.