Phenyl-cyclopentadienyl rule

Abstract

Within a systematic study of cyclic conjugation in the benzo-annelated derivatives of acenaphthylene and fluoranthene, a general regularity was discovered, named phenyl-cyclopentadienyl rule (PCP rule). According to this rule, six-membered rings connected to the five-membered ring by a single carbon-carbon bond increase the magnitude of cyclic conjugation in the five-membered ring. The greater the number of such six-membered rings is, the stronger the cyclic conjugation in the five-membered ring. The PCP rule was initially established by studying the energy effects of individual rings, and was eventually corroborated by a variety of other independent approaches (Wiberg bond orders, carbon-carbon bond lengths calculated by high-level ab initio DFT methods, multicenter delocalization indices, ring currents).