Understanding the differences between iron and palladium in cross-coupling reactions

We aim at developing design principles, based on quantum chemical analyses, for a novel type of iron-based catalysts that mimic the behavior of their well-known palladium analogs in the bond activation step of cross coupling reactions. To this end, we have systematically explored C-X bond activation via oxidative addition of CH3X substrates (X = H, Cl, CH3) to model catalysts mFe(CO)4q (q = 0, -2; m = singlet, triplet) and, for comparison, Pd(PH3)2 and Pd(CO)2, using relativistic density functional theory at the ZORA-OPBE/TZ2P level. We find that the neutral singlet iron catalyst 1Fe(CO)4 activates all three C-X bonds via barriers that are lower than those for Pd(PH3)2 and Pd(CO)2. This is a direct consequence of the capability of the iron complex to engage not only in π-backdonation, but also in comparably strong σ-donation. Interestingly, whereas the palladium complexes favor C-Cl activation, 1Fe(CO)4 shows a strong preference for activating the C-H bond, with a barrier as low as 10.4 kcal mol-1. Our results suggest a high potential for iron to feature in palladium-type cross-coupling reactions.