Mechanistic pathways for oxidative addition of aryl iodides to the low-ligated diethanolamine palladium(0) complex in phosphine-free Heck reactions

A set of reactions of different activated olefins and aryl iodides with the trans-dichlorobis(diethanolamine-N)palladium(II) complex (trans-[PdCl2(DEA)2]) as a precatalyst was performed, in the presence of diethanolamine (DEA) as a weak base, and NaOEt as a strong base. It was established that the presence of NaOEt slightly lowered the yields, but significantly accelerated the reactions. This experimental finding is in agreement with our computational investigation that shows that significantly higher activation barrier is required for the preactivation reaction in the presence of a weak base than in the presence of a strong base. The reaction between the catalytically active DEA–Pd(0)–Cl complex, formed in the preactivation reaction, and iodobenzene was investigated using density functional theory. Two mechanisms for the oxidative addition of the activated complex were found. The first mechanism is based on a nucleophilic attack of Pd on I of iodobenzene, and yields an intermediate tetracoordinated Pd complex (aI2). The second mechanism begins with a nucleophilic attack of Pd on the benzene ring, and yields a tricoordinated intermediate complex (bI4). It was concluded, on the basis of structural and energetical properties of aI2 and bI4, that the second mechanism is significantly more favorable. It was shown that the oxidative addition requires noticeable lower activation energy than that required for the preactivation process. Thus, our investigations indicate that oxidative addition is not the rate determining step for the Heck reactions investigated in this work, but preactivation step.