Complexes of Platinum Group Elements Containing the Intrinsically Chiral Cyclopentadienide Ligand (CpC)−1

Cyclopentadienide derivatives possessing intrinsic helical chirality have only rarely been published in the past. The ligand CpCH, which is well-accessible from inexpensive dibenzosuberenone, is paradigm for such a ligand. Here, the synthesis as well as the spectroscopic and structural characterization of a series of platinum group metal complexes containing this ligand are presented. While alkaline metal salts of CpCH failed in transferring the (CpC)−1 unit to this type of metal sites, (CpC)Tl turned out to be an excellent precursor for the synthesis of ruthenium ([(η5-CpC)­Ru­(η6-arene)]­PF6, [(η5-CpC)­Ru­(NCCH3)3)]­PF6), rhodium ((η5-CpC)­Rh­(η4-COD)), and iridium ((η5-CpC)­Ir­(η4-COD), [(η5-Cp*)­Ir­(η5-CpC)]­PF6) complexes with CpC ligands. EXSY NMR studies were carried out to obtain a deeper insight into the ligand dynamics of CpC complexes.