Dissociation energies of Cα–H bonds in amino acids – a re-examination

Abstract

The C_α–H bond dissociation energies (BDE) in glycine and alanine peptide models have been assessed using selected theoretical methods from the G3 and, in part, G4 family. The BDE values (and thus the stability of the respective C_α peptide radicals) are shown to depend significantly on the level of theory, the size of the model system and the coverage of conformational space. For the largest dipeptide models chosen here, BDE(C_α–H) values of +363.8 kJ mol⁻¹ (glycine) and +372.3 kJ mol⁻¹ (alanine) have been obtained at G3B3 level. This reconfirms earlier findings that glycyl peptide radicals are more stable than radicals derived from alanine or any other amino acid carrying substituents at the C_α position.