Abstract

Background: In continuation from our crusade on the study of ‘attenuation effect' in aromatic and aliphatic systems prompted us to give another attempt to estimate the Taft ρ* value of the dissociation equilibriums (RCH4 + ⇌ RCH3 + H+) of the methanium ion (CH5 +) and substituted methanium ions (RCH4 + ) based on the attenuation effect on the dissociation equilibriums of alkyl ammonium ions (RNH3 + ⇌ RNH2 + H+) with one, two, three, four, five and six atoms between the ionizable proton and the first carbon atom of the substituent.

Objectives: To explain the “attenuation effect” and its applications in organic chemistry to the graduate students.

Methods: All calculations, drawings and curve fittings were done by KaleidaGraph software version 4.1 supplied by Synergy Software INC., Reading, PA, USA.

Results: First the dissociation equilibriums of alkyl ammonium ions with increasing carbon chain length between the ionizable proton and the first carbon atom of the substituent were explained. The Taft ρ* was evaluated for all the equilibriums. Finally the effect of number of atoms between the ionizable proton and the first carbon atom of the substituent were studied. From this the ρ* was evaluated for the equilibrium (RCH4 + ⇌ RCH3 + H+ was evaluated.

Conclusion: Using the application of “attenuation effect” the experimentally not determinable quantities could be determined.

Keywords: Taft reaction constant (ρ*), attenuation effect, methanium ions, super acids, protonation, methananium ions.

Graphical Abstract