Reactions of platinum−argon complexes Pt + Ar m, m = 1−6, with methane (CH 4 ) and methane- d 4 (CD 4 ) were investigated by means of FT-ICR mass spectrometry and DFT calculations. Ligand exchange reactions are observed for Pt + Ar m, m = 2−6, in which up to four argon ligands are replaced by methane. In contrast the bare platinum ion and platinum solvated with one argon ligand lead to the formation of a platinum−carbene complex. Gibbs free enthalpies from ligand exchange reactions of Pt + CH 4 with CD 4 and H 2 O provide evidence for the inserted hydrido−methyl complex HPt + CH 3 which is corroborated by high-level DFT calculations. No isotopic scrambling is observed for the reaction of Pt + CH 4 with CD 4 (and the reverse reaction). This is attributed to the inability of the platinum cation to form more than three covalent bonds.
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Achatz et al. (1999) studied this question.