DFT studies on the distinct mechanisms of C-H activation and oxidation reactions mediated by mononuclear- and binuclear-palladium.

A series of density functional theory calculations have been carried out to investigate the detailed mechanisms of C-H activation and oxidation reactions, and further to disclose the distinct effects of mononuclear- and binuclear-palladium on these reaction pathways. The results of calculations demonstrated that the C-H activation of 2-phenylpyridine with mononuclear Pd(OAc)2 prefers the inner-shell proton-abstraction mechanism, while that with binuclear Pd2(μ-OAc)4 is biased to the outer-shell proton-abstraction mechanism. The rate-determining free-energy barriers of the two mechanisms were calculated to be 24.2 and 24.8 kcal mol-1, respectively. More importantly, we have simulated the oxidation pathways of PdII → PdIII and PdII → PdIV with strong oxidants including PhI(OAc)2, PhICl2 and NCS, and found that a binuclear PdII-precursor would be oxidized to the corresponding binuclear PdIII-complex while a mononuclear PdII-precursor was deemed to evolve to the corresponding mononuclear PdIV-complex. In addition, the oxidation of PdII with PhI(OAc)2 has been characterized as a radical mechanism, in sharp contrast to the ion-pair mechanism prevalent for the oxidation of PdII with PhICl2. The calculated kinetic and thermodynamic parameters could be qualitatively consistent with the related experimental observations. This molecular modelling can provide valuable insights into the understanding of the distinct effects of the resting state and oxidant on these important transformations.