NDLI: Use of molecular electrostatic potential for quantitative assessment of inductive effect

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Suresh, Cherumuttathu H. Alexander, P. Vijayalakshmi, K. Periya Sajith, P. K. Gadre, Shridhar R.
Description	Author Affiliation: Suresh CH ( Computational Modeling and Simulation Section, National Institute for Interdisciplinary Science and Technology (CSIR), Trivandrum 695 019. sureshch@gmail.com)
Abstract	Density functional theory computations at the B3LYP/6-31G(d,p) level have been carried out for three types of model compounds, viz. (i) 4-substituted bicyclo[2.2.2]octane carboxylic acids , (ii) anions of 4-substituted bicyclo[2.2.2]octane carboxylic acids and (iii) 4-substituted quinuclidines where the substituents are $NO_{2},$ CN, Cl, Br, $CF_{3},$ F, CHO, $CH_{2}Cl,$ COOH, $COCH_{3},$ $CONH_{2},$ OH, $OCH_{3},$ $C_{6}H_{5},$ $NH_{2},$ H, $CH_{3},$ $CH_{2}CH_{3},$ $CH(CH_{3})_{2},$ and $C(CH_{3})_{3}$ to study the dependencies between molecular electrostatic potential minimum $(V_{min})$ and the inductive substituent constant $σ_{I}.$ All the three model systems show excellent linear correlation between $V_{min}$ and $σ_{I}$ suggesting that the calculation of $V_{min}$ parameter in these systems offers a simple and efficient computational approach for the evaluation of inductive substituent constants. The calculated linear equation for the models (i), (ii), and (iii) are $V_{min}$ = 12.982 $σ_{I}−$ 48.867, $V_{min}$ = 13.444 $σ_{I}−$ 182.760, and $V_{min}$ = 18.100 $σ_{I}−$ 65.785, respectively. Considering the simplicity of the quinuclidine model, $V_{min}$ value at the nitrogen lone pair region of a 4-substituted quinuclidine system is recommended for the evaluation of $σ_{I}.$ Further, the additivity effect of $σ_{I}$ is tested on multiply substituted quinuclidine and bicyclo[2.2.2]octane carboxylic acid derivatives using the $V_{min}$ approach and the results firmly supported the additivity rule of inductive effect. The systems showing considerable deviations from the additivity rule are easily recognized as those showing either steric effect or intramolecular hydrogen bond interactions at the $V_{min}$ response site. However, the distance relation of $σ_{I}$ is not well represented in the caged molecular systems.
File Format	HTM / HTML
ISSN	14639076
Issue Number	43
Volume Number	10
e-ISSN	14639084
Journal	Physical Chemistry Chemical Physics
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2008-11-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Discipline Physics Discipline Biophysics Discipline Chemistry Carboxylic Acids Chemistry Chemistry, Physical Methods Computer Simulation Hydrogen Bonding Kinetics Ligands Models, Chemical Models, Molecular Molecular Conformation Molecular Structure Static Electricity Journal Article Research Support, Non-u.s. Gov't
Content Type	Text
Resource Type	Article
Subject	Physics and Astronomy Physical and Theoretical Chemistry

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