Attempted thallium triflate abstraction of chloride anions from the MCl2 complexes of the unsaturated chelating diphosphines o-dimethyl-bis(diphenylphosphino)tetrathiafulvalene (P2) (M = Pd, Pt) and cis-1,2-bis(diphenylphosphino)ethylene (dppen) (M = Pd) affords, surprisingly, a TI(OTf) adduct in the case of (P2)PdCl2 and (P2)PtCl2, with no chloride abstraction, and a dicationic bis(palladium) bis(triflate) salt in the case of (cis-dppen)PdCl2, in which only one Cl anion was removed. The crystal structures of these complexes were determined by X-ray analysis, which established the formulations (P2)MCl2.TI(OTf) (M = Pd, Pt) and [(dppen)PdCl](2)(OTf)(2), respectively. These compounds can be seen as possible intermediates in the general chloride abstraction process between (P-P)MCl2 (M = Pd, Pt) and thallium triflate.