Relative stabilities of M/NHC complexes (M = Ni, Pd, Pt) against R–NHC, X–NHC and X–X couplings in M(0)/M(<scp>ii</scp>) and M(<scp>ii</scp>)/M(<scp>iv</scp>) catalytic cycles: a theoretical study

Abstract

The complexes of Ni, Pd, and Pt with N-heterocyclic carbenes (NHCs) catalyze numerous organic reactions via proposed typical M⁰/M^II catalytic cycles comprising intermediates with the metal center in (0) and (II) oxidation states. In addition, M^II/M^IV catalytic cycles have been proposed for a number of reactions. The catalytic intermediates in both cycles can suffer decomposition via R-NHC coupling and the side reductive elimination of the NHC ligand and R groups (R = alkyl, aryl, etc.) to give [NHC-R]⁺ cations. In this study, the relative stabilities of (NHC)M^II(R)(X)L and (NHC)M^IV(R)(X)₃L intermediates (X = Cl, Br, I; L = NHC, pyridine) against R-NHC coupling and other decomposition pathways via reductive elimination reactions were evaluated theoretically. The study revealed that the R-NHC coupling represents the most favorable decomposition pathway for both types of intermediates (M^II and M^IV), while it is thermodynamically and kinetically more facile for the M^IV complexes. The relative effects of the metal M (Ni, Pd, Pt) and ligands L and X on the R-NHC coupling for the M^IV complexes were significantly stronger than that for the M^II complexes. In particular, for the (NHC)₂M^IV(Ph)(Br)₃ complexes, Ph-NHC coupling was facilitated dramatically from Pt (ΔG = -36.9 kcal mol^-1, ΔG^≠ = 37.5 kcal mol^-1) to Pd (ΔG = -61.5 kcal mol^-1, ΔG^≠ = 18.3 kcal mol^-1) and Ni (ΔG = -80.2 kcal mol^-1, ΔG^≠ = 4.7 kcal mol^-1). For the M^II oxidation state of the metal, the bis-NHC complexes (L = NHC) were slightly more kinetically and thermodynamically stable against R-NHC coupling than the mono-NHC complexes (L = pyridine). An inverse relation was observed for the M^IV oxidation state of the metal as the (NHC)₂M^IV(R)(X)₃ complexes were kinetically (4.3-15.9 kcal mol^-1) and thermodynamically (8.0-23.2 kcal mol^-1) significantly less stable than the (NHC)M^IV(R)(X)₃L (L = pyridine) complexes. For the Ni^IV and Pd^IV complexes, additional decomposition pathways via the reductive elimination of the NHC and X ligands to give the [NHC-X]⁺ cation (X-NHC coupling) or reductive elimination of the X-X molecule were found to be thermodynamically and kinetically probable. Overall, the obtained results demonstrate significant instability of regular Ni/NHC and Pd/NHC complexes (for example, not additionally stabilized by chelation) and high probability to initiate "NHC-free" catalysis in the reactions comprising M^IV intermediates.