Intramolecular C–H insertion using NHC–di-rhodium(II) complexes: the influence of axial coordination

In this work we show that the intramolecular C–H insertion of diazo-acetamides catalysed by di-rhodium(II) complexes can be highly influenced by the axial ligand on the di-rhodium(II) complex. Axially monocoordinated NHC–Rh2(OAc)4 complexes have a distinct reactivity from the parent Rh2(OAc)4 complex affording the cyclisation products in different rates and selectivities. Surprisingly, a new reaction mode emerged when using these complexes which led to a decarbonylation pathway.