Rational Design of Cyclopentadiene-Based Super- and Hyperacids Based on Aromaticity

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 128; no. 35; pp. 7384 - 7395
• Main Authors: Si, Mrinal Kanti, Shigeta, Yasuteru
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 05.09.2024
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.4c03786

The design and synthesis of neutral organic superacids have been of interest recently due to their vast applications in chemistry and material sciences, for example, olefinic polymerization, isolation of highly reactive short-lived cations, etc. Cyclopentadiene behaves as a mild organic acid, producing a stable conjugate base by gaining aromaticity and conjugation after deprotonation. To stabilize conjugate bases of organic acids to show superacidities and hyperacidities, we considered aromatic phenyl substituents with cyclopentadiene (mono-, di-, and triphenyl-substituted cyclopentadiene and their cyano derivatives). The MP2, DFT (B3LYP, M06-2X), and CBS-QB3 methods were used to calculate the gas-phase proton affinities of the parent cyclopentadiene, and the DFT methods were chosen for the substituted cyclopentadiene as they yield an experimental proton affinity of cyclopentadiene of 253.66 kcal/mol (Expt. 253.6 ± 1.3 kcal/mol). The stable trisubstituted cyclopentadiene derivative shows gas-phase enthalpies of deprotonation (ΔH acid) of 245 and 239 kcal/mol with DFT B3LYP and M06-2X methods, respectively, with values in the range of hyperacidity. Some of the tautomers of cyclopentadiene derivatives show hyperacidity, with proton affinity values of 205–240 kcal/mol. Triphenyl-substituted cyclopentadiene behaves as a moderate acid but transforms into a superacid after replacing the phenyl group with nitrobenzene, which is a stronger acid than H2SO4 (ΔH acid = 298 kcal/mol). The nucleus-independent chemical shift (NICS) shows the extent of conjugation in the derivatives of cyclopentadienyl anions after deprotonation, which affects the stabilities of conjugate bases, i.e., the acidities of the protonated species. The calculated harmonic oscillator model of aromaticity and NICS indices reveal that the stability of conjugate bases as well as their acidities increase with increasing aromaticity of cyclopentadiene rings after deprotonation in all molecules.