Theoretical Considerations Concerning Hammett's Equation. IV. Calculation of ρ-Values
- 1 March 1953
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 21 (3) , 415-419
- https://doi.org/10.1063/1.1698922
Abstract
The assumption is made that the effect of a meta or para substituent X on the reactivity of a reacting center Y in a compound [Complex chemical formula] depends only on the electron density change induced by the substituent in the atom at which Y is attached to R. Using this assumption relative values of Hammett's reaction constant (ρ) are calculated for a given reaction in several series of compounds having the above formula. The calculations require the computation of the electron density changes induced by substituents in the atom at which Y is attached to R. The computations are carried out by the semiempirical LCAO MO method for several cases where R and the benzene ring form part of a single conjugated system. The resulting relative ρ‐values are compared with experimental data. Reasonable agreement is found.Keywords
This publication has 8 references indexed in Scilit:
- Ionization Constants and Rates of Ester Hydrolysis in the Benzylidenepyruvic Acid SeriesJournal of the American Chemical Society, 1952
- The Ionization Constants of Some p-Substituted p'-Dimethylaminoazobenzenes1Journal of the American Chemical Society, 1951
- A Nuclear Magnetic Parameter Related to Electron Distribution in MoleculesThe Journal of Chemical Physics, 1951
- Some Studies in Molecular Orbital Theory I. Resonance Structures and Molecular Orbitals in Unsaturated HydrocarbonsThe Journal of Chemical Physics, 1950
- The electronic structure of conjugated systems II. Unsaturated hydrocarbons and their hetero-derivativesProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1947
- The electronic structure of conjugated systems I. General theoryProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1947
- The Calculation of the Ionization Constants of Inorganic Oxygen Acids from their StructuresJournal of the American Chemical Society, 1938
- A Quantum Mechanical Discussion of Orientation of Substituents in Aromatic MoleculesJournal of the American Chemical Society, 1935