IUPAC > Gold Book > alphabetical index > E > electronic effect of substituents: symbols and signs
icon


Indexes

electronic effect of substituents: symbols and signs
The inductive effect has universally been represented by the symbol Math - text. This is now commonly taken to include both through-bonds and through-space transmission, but Math - text is also used specifically for through-bonds transmission; through-space transmission is then symbolized as Math - text (for field effect). The symbols for the influence of substituents exerted through electron delocalization have variously been Math - text (mesomeric), Math - text (electromeric), Math - text (tautomeric), Math - text (conjugative), K (konjugativ) and Math - text (resonance). Since the present fashion is to use the term resonance effect, Math - text is the most commonly used symbol, although Math - text is still seen quite often. Both the possible sign conventions are in use. The Ingold sign convention associates electronegativity (relative to hydrogen atom) with a negative sign, electropositivity with a positive sign. Thus the nitro group is described as electronwithdrawing by virtue of its Math - text and Math - text effects; chloro is described as a Math - text, Math - text substituent, etc. For correlation analysis and linear free-energy relationships this convention has been found inconvenient, for it is in contradiction to the sign convention for polar substituent constants (σ-constants). Authors concerned with these fields often avoid this contradiction by adopting the opposite sign convention originally associated with Robinson, for electronic effects. This practice is almost always associated with the use of R for the electron delocalization effect: thus the nitro group is a Math - text, Math - text substituent; chloro a Math - text, Math - text substituent, etc.
Source:
PAC, 1994, 66, 1077 (Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)) on page 1111
Interactive Link Maps
First LevelSecond LevelThird Level
GraphGraphGraph
Cite as:
IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A.Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. doi:10.1351/goldbook.
DOI of this term: doi:10.1351/goldbook.E01996
Original PDF version (may be out of date): http://www.iupac.org/goldbook/E01996.pdf.
Version for print | History of this term
picture