[(CO)2Pt(CH3)2], [(PF3)2Pt(CH3)2], and [(CF3)2PC2H4P(CH3)2Pt(CH3)2] [dfmpe = (CF3)2PC2H4P(CF3)2] are obtained by ligand exchange reactions. The thermal stability of the complexes increases in the given sequence, whereas their volatility decreases. Demethylation reactions with anhydrous HF cleave one methyl group. The addition of AsF5 and SbF5 often cleaves both methyl groups. The resulting L2Pt2+ compounds are obtained in crystalline form with the corresponding [AsF6]–, [SbF6]–, [Sb2F11]–, and [B12F12]2– anions. Bridged dimeric or trimeric platinum complexes are also formed.