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A Semi‐Empirical Model of the Energy Barrier of Proton Transfer Reactions
Author(s) -
Willi Alfred V.
Publication year - 1971
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19710540432
Subject(s) - chemistry , proton , kinetic isotope effect , ionic bonding , hydrogen bond , computational chemistry , resonance (particle physics) , moiety , bond order , thermodynamics , ion , crystallography , deuterium , atomic physics , stereochemistry , molecule , bond length , organic chemistry , quantum mechanics , physics
The energy barrier in proton transfer reactions is described by a Johnston ‐type equation (1) ( n = order of bond to be broken). The barrier model is discussed in terms of free energies. The V i values are free energies of ionic cleavage in aqueous solution of the XH and YH bonds; they are computed from eqns. (4c) and (4d). The values of p 1 and p 2 affect curvature (absence or presence of maximum) and symmetry of the barrier. It is postulated that p i is a typical constant of the reacting bond and can be transferred from one transition state to another. With the aid of eqn. (1) and its first derivative, values of p i and n m (bond order at maximum of barrier) can be based on quantities determined experimentally, Δ≠ and ΔG. For OH bonds, pi ≈ 1.0. For CH bonds p i is larger than 1.0 and depends on the structure of the carbanionic moiety (influence of resonance and inductive effects). As there cannot be a maximum if p 1 = p 2 = 1.0, the suggested model of the barrier leads to a better understanding why proton transfer must be ‘fast’ in some reactions and ‘slow’ in others. The computed values of n m may be utilized to gain some insight into the nature of the transition states; they supply a basis for the discussion of primary hydrogen isotope effects.