Reaction of Coordinated Phosphines. III. Reaction of Phenyl Compounds of Typical Groups V and VI Elements with Palladium(II) Salts in the Presence of Olefinic Compounds

The reaction of phenyl compounds of typical groups V and VI elements, PhnA and PhnAX2 (n=2, 3; A=P, As, Sb, Bi, S, Se, Te; X=Cl or X2=O), with Pd(II) salts was studied in the presence of olefinic compounds (1-octene and ethyl acrylate) in acetonitrile. The phenyl migration from A to Pd to produce phenylpalladium species, which lead to the phenylation of olefin, was observed for all PhnA and PhnAX2 (except for A=S and Ph3PX2) when Pd(OAc)2 was utilized. The reaction, however, was inhibited or greatly suppressed for the compounds of P and As when PdCl2 was used in place of Pd(OAc)2. The compounds of Sb and Bi readily react with PdCl2. Mechanistic discussion was given in terms of the extent of nucleophilic assistance by acetate ion when Pd(II) attacks the aromatic nucleus electrophilically at the carbon atom bonded to A.