Menschutkin reactions of aliphatic diamines with methyl iodide in acetonitrile–methanol mixtures. Evaluation of the role of the non-reacting nitrogen atom

Kinetic and thermodynamic analyses have been performed for the reactions of aliphatic diamines with methyl iodide in acetonitrile–methanol mixtures. Solvation patterns around non-reacting nitrogen atoms have been evaluated for activated complexes and for product cations. These analyses enable the two transition-state indices due to physical interaction, i.e. extended Bronsted coefficients, αPHYS and isokinetic temperatures, βPHYS to be determined. An empirical correlation between βPHYS and αPHYS multiplied by the dipole moment of an initial state, has been found, and the physical significance of the correlation is discussed. Multiple use of transition-state indices and their empirical analyses are indispensable for characterizing the particular roles played by non-reacting nitrogen atoms in these reactions.