Synthesis and a combined experimental/theoretical structural study of a comprehensive set of Pd/NHC complexes with o-, m-, and p-halogen-substituted aryl groups (X = F, Cl, Br, CF3)

Abstract

Pd/NHC complexes (NHCs – N-heterocyclic carbenes) with electron-withdrawing halogen groups were prepared by developing an optimized synthetic procedure to access imidazolium salts and the corresponding metal complexes. Structural X-ray analysis and computational studies have been carried out to evaluate the effect of halogen and CF₃ substituents on the Pd–NHC bond and have provided insight into the possible electronic effects on the molecular structure. The introduction of electron-withdrawing substituents changes the ratio of σ-/π-contributions to the Pd–NHC bond but does not affect the Pd–NHC bond energy. Here, we report the first optimized synthetic approach to access a comprehensive range of o-, m-, and p-XC₆H₄-substituted NHC ligands, including incorporation into Pd complexes (X = F, Cl, Br, CF₃). The catalytic activity of the obtained Pd/NHC complexes was compared in the Mizoroki–Heck reaction. For substitution with halogen atoms, the following relative trend was observed: X = Br > F > Cl, and for all halogen atoms, the catalytic activity changed in the following order: m-X, p-X > o-X. Evaluation of the relative catalytic activity showed a significant increase in the catalyst performance in the case of Br and CF₃ substituents compared to the unsubstituted Pd/NHC complex.