Competitive Intramolecular Aryl- and Alkyl-C-H Bond Activation and Ligand Evaporation from Gaseous Bisimino Complexes [Pt(L)(CH3)((CH3)2S)]+ (L=C6H5N=C(CH3)-C(CH3)=NC6H5)

Mechanistic details for the formation of methane from the title compound as well as the combined elimination of (CH3)(2)S/CH4 are derived from various mass-spectrometric experiments including deuterium-labeling Studies and DFT calculations. For the first process, i.e.. methane formation, we have identified three competing pathways in which the intact, Pt-bonded methyl group combines with a H-atom that originates from a phenyl substituent (ca. 7%), the dimethyl sulfide ligand (ca. 41%), and a methyl group of the diazabutadiene backbone (ca. 52%). In contrast. in the combined (CH3)(2)S/CH4 elimination. the methane is specifically formed from the Pt-bound CH3 group and a H-atom provided by one of the phenyl groups ('cyclometalation').