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Residual electronegativity - an empirical quantification of polar influences and its application to the proton affinity of amines

✍ Scribed by Michael G. Hutchings; Johann Gasteiger


Publisher
Elsevier Science
Year
1983
Tongue
French
Weight
236 KB
Volume
24
Category
Article
ISSN
0040-4039

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✦ Synopsis


The residual electronegativity of an atom in a molecule can be used as a quantitative mecsure odf the polar influence of a substituent on reactivity, as exemplifiedby its ability, with substituent polarisability, to coTrelate the proton affinity data of 80 amines.

A cornerstone of organic chemistry is

the notion that there exist fundamental relationships between the structure of a molecule and its chemical reactivity. Concepts like inductive, resonance, steric, polarisability and solvent effects have been invoked in a qualitative manner, whereas the quantitative treatment has centred around linear free energy relationships (LFER). With LFER, correlations are sought between two sets of reactivity data, the reaction under investigation, and a standard one. Although this empirical approach has been quite successful some serious problems still exist. The artificial separation of a structure into substituent, skeleton