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Updated: Jul 14, 2026

Determination of the Gas-phase Acidities of Oligopeptides
Published on: June 24, 2013
Can changes in one-bond spin-spin coupling constants in acids be related to gas-phase proton affinities of bases?
Janet E Del Bene1, José Elguero
1Department of Chemistry, Youngstown State University, Youngstown, Ohio 44555, USA. jedelbene@ysu.edu
Abstract:
Ab initio EOM-CCSD calculations have been carried out in search of acids with one-bond spin-spin coupling constants which could serve as probes of molecular basicity upon complex formation. Only 1J(F-H) and 1J(B-Li) in complexes F-H...Y and H2B-Li...Y, respectively, are able to differentiate among the protonation energies of bases containing Y. Changes in 1J(F-H) upon complex formation are related to the protonation energies of bases, but only when these energies are about 200 kcal/mol or greater. On the other hand, changes in 1J(B-Li) upon complexation are related to base protonation energies in the range between 100 and about 190 kcal/mol. Thus, these two one-bond coupling constants 1J(F-H) and 1J(B-Li) are complementary probes. For the first time, the computed NMR property of a gas-phase one-bond spin-spin coupling constant has been related to the experimental gas-phase thermodynamic property of proton affinity.
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