Evidence for a Cooperative Mechanism Involving Two Palladium(0) Centers in the Oxidative Addition of Iodoarenes.

Oxidative addition of iodoarenes (ArI) to Pd0 ligated by 1-methyl-1H-imidazole (mim) in polar solvents leads to cationic arylpalladium(II) complexes [ArPd(mim)3 ]+ . Kinetic analyses evidence that this reaction is second order with respect to the concentration of Pd0 , and a mechanism involving the cooperative intervention of two Pd0 centers has been postulated to explain this finding. This unusual behavior is also observed with other nitrogen-containing ligands and it is general for iodobenzenes substituted with electron-donating or weakly electron-withdrawing groups. In contrast, bromoarenes and electron-poor iodoarenes display first-order kinetics with respect to Pd0 . Theoretical calculations performed at the density functional theory (DFT) level suggest the existence of mim-ligated ArI-Pd0 complexes, in which the iodoarene is bound to the metal in a halogen-bond-like fashion. Coordination weakens the C-I bond and facilitates the oxidative insertion of another Pd0 center across this C-I bond. This conceptually novel mechanism, involving the cooperative participation of two distinct metal centers, allows a full explanation of the experimentally observed kinetics.