Hydride Affinities of Some Substituted Alkynes: Prediction by DFT Calculations and Rationalization by Triadic Formula

Hydride affinities (HAs) of the ethynes substituted by a wide range of different substituents are considered by using the B3LYP methodology. The computed values are in fair agreement with available experimental data, which are unfortunately scarce. The trend of changes of the HAs is rationalized by trichotomy formula. One of the important results of this analysis is a finding that similar HA values might result from completely different effects. Alternative sites of the H- attack are examined and the difference in energies relative to the most susceptible positions is interpreted. Structural features of substituted ethyne hydrides are briefly discussed.