Unexpected Reactivity of PdCl<sub>2</sub> and PtCl<sub>2</sub> Complexes of the Unsaturated Diphosphine <i>o</i>-Me<sub>2</sub>TTF(PPh<sub>2</sub>)<sub>2</sub> toward Chloride Abstraction with Thallium Triflate
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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 Tl(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·Tl(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.
