Synthesis and reactivity of anionic mono- and binuclear pentachlorophenyl complexes of palladium(II) and platinum(II)

Article abstract of DOI:10.1021/om50004a023

Arylation with C₆Cl₅Li or C₆Cl₅MgCl of several palladium or platinum substrates leads to new mono-or binuclear complexes of type [MR₄]^2-, [M₂(μ-X)₂R₄]^2-, or [trans-PtCl₂R₂]^2- (M = Pd or Pt; R = C₆Cl₅; X = Cl or Br) which have been isolated as tetraalkylammonium salts. Treatment of the anionic binuclear complexes with stoichiometric amounts of the ligand L produces anionic mononuclear derivatives of the type [cis-MClR₂L]^- (M = Pd or Pt; R = C₆Cl₅; L = PPh₃, PEt₃, py, or SbPh₃) while the use of an excess of the ligand L affords the neutral derivatives cis-MR₂L₂ (M = Pd or Pt; R = C₆Cl₅; L = PPh₃, PEt₃, PPh₂Me, py, or SbPh₃; L₂ = bpy, dpe, or dae). The reactions of the binuclear complexes [M₂(μ-X)₂R₄]^2- with halides or pseudohalides give rise to substitution of the bridging halides (without cleavage of the bridges) and to the formation of [M₂(μ-X′)₂R₄]^2- (X = Cl; X′ = Br, I, or SCN). [MR₄]^2- reacts with the appropriate amount of HCl to give high yields of the anionic binuclear complexes [M₂(μ-Cl)₂R₄]^2-. These compounds are the first anionic palladium or platinum complexes containing the pentachlorophenyl group to be reported.