Collision-induced dissociation (CID) of the mass-selected cation [(bipy)Pt(CH3)2(CH2SCH3)]+ in an ion-trap mass-spectrometer results in the losses of the neutrals ethane, ethene, dimethyl sulfide, methane, ethyl methyl sulfide, and propane. The generation of the first four neutrals is also observed, when the isolated, dimeric complex [(bipy)Pt(CH3)2(CH2SCH3)]2[SbF6]2 is heated in the condensed phase. While the product distribution is very similar regardless of whether the complex is heated in the solid state or in solution, ethane loss, i.e. the quite rare event of an sp3-sp3 C–C reductive elimination from a platinum(IV) complex, dominates in the gas-phase experiment. However, when the counter anion [SbF6]- is exchanged by the more weakly coordinating anion [BAr4F]-, the amounts of ethane and ethene are increased also in the condensed phase. These sum of observations indicates the similarities of the fragmentation of [(bipy)Pt(CH3)2(CH2SCH3)]+ in both phases. Thus, a correlation of processes in both environments is possible for selected systems (and particularly for unimolecular processes), but the choice of the proper conditions is crucial for a meaningful comparison.