Density functional B3LYP calculations have been employed to investigate the reaction of platinum oxide with methane. NO is shown to form a molecular complex with CH4 bound by similar to13 kcal/mol. At elevated temperatures, direct abstraction of a hydrogen atom is possible leading to PtOH and free methyl radical with a barrier of similar to26 kcal/mol. A minor reaction channel is insertion into a C-H bond to produce a CH3PtOH molecule, which can be also formed by recombination of PtOH and CH3. CH3PtOH would preferably dissociates through a mechanism involving 1,2-CH3 migration to produce a PtCH3OH complex and eventually Pt + CH3OH. (C) 2002 Elsevier Science B.V. All rights reserved.