Mono- and bi-nuclear anionic pentafluorophenyl complexes of palladium(<scp>II</scp>) and platinum(<scp>II</scp>)

The arylation of K2[MCl4], [MCl2(tht)2], MCl2, or [NBu4]2[M2(µ-Br)2Br4](M = Pd or Pt; tht = tetrahydrothiophen) with LiR or MgBrR (R = C6F5) leads to novel mono- and bi-nuclear anionic organo-derivatives of the general formulae [MR3(tht)]–, [MR4]2–, and [M2(µ-Br)2R4]2–, which have been isolated as tetra-alkylammonium salts. Reaction of compounds of the [MR3(tht)]– type with neutral ligands leads to the substitution of tht by L, that of [PdR4]2– with PdCl2 gives rise to the formation of [Pd2(µ-Cl)2R4]2–, whilst [M2(µ-X)2R4]2– reacts with alkali-metal salts of Br–, I–, or SCN– to give (without cleavage of the bridging system) the corresponding complexes. Twenty anionic complexes of these three novel types have been isolated and characterized.