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

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Abstract

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.

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

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Publication details

The article was received on 15 Dec 2018, accepted on 22 Feb 2019 and first published on 25 Feb 2019


Article type: Paper
DOI: 10.1039/C8CP07671E
Citation: Phys. Chem. Chem. Phys., 2019, Advance Article

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

    X. Sun, M. V. J. Rocha, T. A. Hamlin, J. Poater and F. M. Bickelhaupt, Phys. Chem. Chem. Phys., 2019, Advance Article , DOI: 10.1039/C8CP07671E

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