Reaction mechanisms for C-O bond coupling from Pt4CH2+ and O-2: A relativistic density functional study
- 化学化工－已发表论文 
Computational investigations on the reaction of Pt4CH2+ with O-2 have been carried out by the relativistic density functional approach. Calculations indicate that the reactivity Of Pt4CH2+ toward O-2 is different from the metallic carbene PtCH2+. The dehydrogenation route in the reaction of Pt4CH2+ with O-2 is quite unfavorable, both dynamically and thermodynamically. The reaction channels to products H2O/CO and HCOOH with involvement of O-O bond activation and C-O bond coupling are strikingly exothermic, where the C-O bond coupling and the release of CO are the crucial steps for the entire reaction channels. Predicted overall Gibbs free energies of reaction Delta G are -66.2 kcal mol(-1) for H2O/CO and -73.5 kcal mol(-1) for HCOOH, respectively. Both energy-favored routes have thus relatively high reaction efficiencies toward O-2 in comparison with dehydrogenation. On the basis of theoretical results, plausible mechanisms for the reaction of Pt4CH2+ with O-2 and candidates for the experimental neutral products [C, H-2, O-2] in reaction have been proposed.