Decomposition of the product of methoxypalladation of dichloro(2,2-dimethylbut-3-enyl methyl sulphide)palladium (II). Identification of an α-alkoxyalkylpalladium(II) intermediate

Abstract

The methoxypalladation product [{[graphic omitted]Me]}₂] from the title complex (3) undergoes relatively slow decomposition in solution via at least two pathways. The major pathway leads to complexes containing the acetal MeSCH₂CMe₂CH₂CH(OMe)₂ or the corresponding aldehyde. An important intermediate in this pathway is the α-methoxyalkylpalladium(II) derivative [{[graphic omitted]Me]}₂] which has also been generated by reaction of McSCH₂CMe₂CH₂CH(Cl)OMe with bis(dibenzylideneacetone) palladium (0). The minor pathway involves hydride transfer between ligand molecules and leads to complexes containing both oxidised and reduced ligands. More efficient hydride transfer is observed when the product [{[graphic omitted]Me]}₂] from reaction of (3) with HgPh₂ is treated with McSCH₂CMe₂CHCH₂.