Facile Addition and Elimination Reactions of Fluorocarbon Acids at Platinum

Article abstract of DOI:10.1021/ja00264a032

Reaction of the fluorocarbon acid H2C(SO2CF3)2 with (Ph3P)2Pt(C2H4) yields trans-(Ph3P)2PtH in which restricted rotation about a covalent Pt-C bond was demonstrated by multinuclear NMR spectroscopy.This compound rearranges to the cis isomer by first-order kinetics and is rapidly solvolyzed by Lewis bases to afford trans-(Ph3P)2PtHL⁺-HC(SO2CF3)2^- (L = CH3CN, DMF, CH3OH, H2O, and THF).Complexes containing weak Lewis bases (THF and CH3OH) are unstable and dimerize to form (Ph3P)3Pt2(μ-H)(μ-PPh2)Ph⁺HC(SO2CF3)2^- , a = 14.039(2) Angstroem, b = 20.318(3) Angstroem, c = 13.626(3) Angstroem, α = 94.43(1) deg, β = 95.69(1) deg, γ = 77.47(1) deg, Z = 2, R = 0.059>.Solvolysis of the cis isomer is slower by a factor of ca. 18.