Substituent-induced polarization of charge in phenalenyl anions

Abstract

The effect of trimethylsilyl, alkynyl and cyano substituents on the charge distribution of the phenalenyl anionic nucleus was examined using semiempirical calculations and NMR spectroscopy. With these techniques it was demonstrated that the trimethylsilyl and cyano substituents are capable of attracting adjacent negative charge. Examples of reactions from the literature confirm the charge-attracting capabilities of the trimethylsilyl substituent. The alkynyl substituent was shown to perturb the charge distribution of the phenalenyl moiety to a much lesser degree than the vinyl substituent in the 1-hydropyrenyl anion.

Polyarene anions: interplay between theory and experiment

“…The group of Cornelisse has studied polycyclic anions sharing a phenalenyl moiety, and their reactivity toward electrophilic substitution by α , ω ‐haloalkanes and other electrophiles 88–90. Mulliken charge distribution and MOs were calculated parametrized model number 3 (PM3) for the phenalenyl and benzathrenyl anions, as well as some of their derivatives.…”