A systematic review and new approach to the syntheses of the Group VI and Group VIII transition metal derivatives of the pentaphenyl-cyclopentadienyl ligand are described. Significant enhancement in stability and reactivity of these perphenylated complexes is observed when compared to cyclopentadienyl and peralkylatedcyclopentadienyl derivatives due to their much higher molecular weights, reduced volatility, and modified solubility. These compounds have proved to be easily synthesized from the now readily available starting material, pentaphenylcyclopentadiene. Numerous physical and spectral properties as well as the x-ray crystal structure of a ruthenium derivative are reported.