DFT study of inter-ring haptotropic rearrangement in CpRu+ complexes of polycyclic aromatic ligands

Abstract Inter-ring haptotropic rearrangements (IRHRs) of different types are well-known phenomena in organometallic and catalytic chemistry. So far, they are reported for transition metal complexes with carbo- and heterocyclic polyaromatic hydrocarbons (PAH) of small and medium size. Here, we report DFT studies of RuCp + shifts between neighboring six-membered rings (η 6 ⇌ η 6 -IRHR) on an extra-large PAH as a model for graphene and compare it to naphthalene. Our calculations predict that η 6 ⇌ η 6 -IRHRs proceed with much lower activation energy barrier of rearrangement in the case of the RuCp + complex of η 6 -graphene model.