A novel approach to the analysis of substituent effects: quantitative description of ionization energies and gas basicity of amines.
In this work, a new topological approach based on simple matrix algebra is introduced to explore substituent effects at the level of atomic additivity in the absence of significant resonance contributions. In the framework of the suggested method, all atoms are classified according to element and valence state. The sums of the inverse squared distances between the substituent atoms and the reaction centre of the molecule are used as operational parameters in the present method. The approach implies atomic level of consideration of inductive and steric effects and allows for quantification of substituent effects without the use of pre-established group substituent constants. The practical application of the model is illustrated by the quantitative interpretation of ionization energies and gas basicity of a broad range of amines. Further development of the elaborated approach is also discussed.
Cherkasov
A R
AR
Department of Chemistry, Royal Institute of Technology, Stockholm, Sweden. art215@duke.usask.ca
Jonsson
M
M
Galkin
V
V
D000588:Amines / Q000737:chemistry*; D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry; D005740:Gases / Q000737:chemistry*; D012984:Software; D055672:Static Electricity; D013223:Statistics as Topic; D013329:Structure-Activity Relationship
D000588:Amines; D005609:Free Radicals; D005740:Gases