{Rh(PiBu3)2}+ Fragments Ligated to Arenes: From Benzene to Polyaromatic Hydrocarbons, Part I – An Experimental Approach

We report the synthesis, structural characterisation andsolution‐phase dynamics of a series of polyaromatic hydrocarbon complexes of the 12‐electron {Rh(PiBu3)2}+ fragment. Crystal structures of this fragment with benzene, naphthalene, anthracene, pyrene, triphenylene and coronene are described, alongside their solution NMR spectroscopic data. The ligands map out a systematic increase in size of the aromatic subunit, and represent an approach to the limiting case of coordination to a graphene surface. The solid‐state and solution structures of a {Rh(COD)}+ fragment coordinated to a hexa‐peri‐hexabenzocoronene are also reported.