Lewis acid catalysis of the rearrangement of a dipalladium acetylene adduct to a vinylidene-bridged complex

Article abstract of DOI:10.1021/om00009a031

The crystallographically characterized vinylidene complex [Pd₂Cl₂(μ-dppm)₂(μ-σ-C=C-(SCH ₃)₂)] (3); dppm = bis(diphenylphosphino)methane) was prepared by the reaction of [Pd₂-Cl₂(μ-dppm)₂] with CH₃SC≡CSCH₃ in the presence of HBF₄·Et₂O as well as through an isomerization of the acetylene adduct [Pd₂Cl₂(μ-dppm)₂(μ-CH ₃SCCSCH₃)] (1) catalyzed by several Lewis acids. Treatment of the related acetylene adduct [Pd₂Cl₂(μ-dmpm)₂(μ-CH ₃-SCCSCH₃)] (2; dmpm = bis(dimethylphosphino)methane) with HBF₄·Et₂O yielded the tetranuclear palladium complex [Pd₄(μ-Cl)₂(μ-dmpm)₂(μ-SCH ₃)₄][BF₄]₂ (4), which was also characterized crystallographically.