Remote secondary deuterium kinetic isotope effects as a probe of steric strain in the solvolysis of tertiary alkyl carbinyl systems

Abstract

12) Arnett and Taft3 on the basis of extrathermodynamlc considerations were able to separate the hydrogen-bonding part of the water solvation of the pyridinium Ions from the other terms (cavity formation and structural changes In solvent). However, for cyanopyrldlne the óAFF 'Hi0 = -4.8 kcal/mol Is almost Identical with the 0 6 "-0 due to H bonding only, which is -5 kcal/mol.(13) E.