Ring-expanded N-heterocyclic carbenes as ligands in iron-catalysed cross-coupling reactions of arylmagnesium reagents and aryl chlorides

Abstract

The structure–activity relationship of expanded-ring N-heterocyclic carbenes (NHCs) in the iron-catalysed Kumada aryl–aryl coupling reaction was explored. This was achieved by comparing the catalytic performance of Fe-NHC catalysts generated in situ containing NHCs that differ in steric bulk. In particular, the influences of ring sizes (5–8) and N-aryl substituents were explored in terms of spectroscopic and structural features, which affect their %V_bur values. The three best performing ligands were found on a diagonal of a 5 × 4 structural matrix revealing an optimal steric bulk and significant influences of subtle steric variations on the catalytic activities.