Appraisal of Through-Bond and Through-Space Substituent Effects via Molecular Electrostatic Potential Topography

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 114; no. 46; pp. 12330 - 12333
• Main Authors: Sayyed, Fareed Bhasha, Suresh, Cherumuttathu H., Gadre, Shridhar R.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 25-11-2010
• Subjects: A: Molecular Structure, Quantum Chemistry, General Theory; Hydrocarbons, Aromatic - chemistry; Hydrocarbons, Aromatic - metabolism; Models, Chemical; Molecular Structure; Static Electricity
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp107689z

Through-bond (TB) and through-space (TS) substituent effects in substituted alkyl, alkenyl, and alkynyl arenes are quantified separately using molecular electrostatic potential (MESP) topographical analysis. The deepest MESP point over the aromatic ring (V min) is considered as a probe for monitoring these effects for a variety of substituents. In the case of substituted alkyl chains, the TS effect (79.6%) clearly dominates the TB effect, whereas in the unsaturated analogues the TB effect (∼55%) overrides the TS effect.