Mechanistic control by the size of the outgoing group in a palladium(II) substitution reaction
Abstract
Kinetic studies of the substitution reactions of [Pd(1,1,7,7-tetraethyldiethylenetriamine)XCN]+ with bromide ion in dimethylformamide indicate that, for X = S, an SNI or solvent-assisted ligand interchange process is operative whereas, for X = Se, a concurrent SN2 path involving chelate ring-opening is also involved—a unique example of mechanistic control by an outgoing group.