Gas-Phase Acidities of Cycloheptatrienes: Effects of Alkyl Groups on the Stability of Carbanions

Abstract

The gas-phase acidities of 7-alkyl substituted cycloheptatrienes have been determined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry using a proton-transfer equilibrium method, Δ G0acid (kJ mol−1): methyl 1520.0, ethyl 1516.7, n-propyl acid 1513.3, i-propyl 1512.1, n-butyl 1510.4. The effect of alkyl groups on the acidity of cycloheptatriene is linearly correlated with the polarizability parameters ( σα) of substituents, giving a ρα of–55.3 (kJ σ−1α unit). The magnitude of pa is half of that for RCH3 and is significantly larger than that for the fluorene series. These results suggest that the extent of the charge-delocalization in a carbanion plays an important role in determining the susceptibility of the stability of the carbanion to substituent polarizability effects. In addition, comparison of ρ values of acidities of a series of elemental hydrides shows that the numerical value of ρα decreases in the order, C > O ≈ N > S, and that the change of ρα is related to the stability of the respective parent anions (R = H) rather than the atomic electronegativity at the deprotonation center.