IZCp and PZCp: Redox Non-innocent Cyclopentadienyl Ligands as Electron Reservoirs for Sandwich Complexes

A long-sustained effort of systematic steric and electronic modification of cyclopentadienyl (Cp) ligands has enabled them to find wide-ranging, valuable applications. Herein, we present two novel Cp ligands: imidazolium- and pyrrolinium-substituted zwitterionic Cps (IZCp and PZCp), whose key utility is redox non-innocence & horbar;the ability to participate cooperatively with the metal center in redox reactions. Through the simple metalation of ZCps, the Cr(0) and Mo(0) half-sandwich complexes (IZCp)Cr(CO)(3), (PZCp)Cr(CO)(3), (IZCp)Mo(CO)(3), and (PZCp)Mo(CO)(3), respectively, as well as the Ru(II) sandwich complexes [(IZCp)RuCp]PF6 and [(PZCp)RuCp]PF6 were prepared. The sandwich complexes were fully characterized and showed by cyclic voltammetry reversible one-electron reduction at E-1/2 potentials ranging from -1.7 to -2.7 V vs Fc/Fc(+). These values are unusually low and have not been observed with other Cp ligands due to the instability of the reduced complexes. Density functional theory (DFT) calculations for the reduced sandwich derivatives with IZCp and PZCp showed their spin densities to be highly delocalized over their ZCp ligand moieties (70-90%). Electron paramagnetic resonance (EPR) analysis of the isolated K[(PZCp)Mo(CO)(3)] and (PZCp)RuCp also indicated a high degree of ligand-localized radical character. Thus, the IZCp and PZCp ligands act as electron reservoirs to sustain these sandwich complexes in highly reduced states. At the same time, the CO stretching frequencies of K[(PZCp)Mo(CO)(3)]: nu(CO) 1871, 1748, and 1699 cm(-1), rank the [PZCp](-) ligand as the strongest electron-donating Cp ligand among the reported CpMo(CO)(3) derivatives, whose nu(CO) > 1746 cm(-1). In addition, these redox non-innocent Cps were obtained in high yields and found to be practically air- and moisture-stable, unlike typical Cps.