1. Kinetics and mechanism. Salt effects and common ion rate depression.
2.Non-kinetic methods. Stereochemical studies of the nucleophilic substitution of tetracordinated carbons. Stereochemical tools for the determination of the stereoselectivity of reactions. Crossover experiments. Isotopic labelling.
3.Substituent effects. Inductive (field) effects through bonds and through space. Stereoelectronic effects. Steric effects. Attractive van der Waals interactions.
4.Hammett equation. Applications of the Hammett equation to mechanistic studies. Rho values of two-step reactions. Nonlinearity of Hammett plots (minimum and maximum). Sigma, sigma(+) and sigma(-) values.
5.Steric effects of substituents. Es values.
6.Acid and bases.Kinetic and thermodynamic acidity. Solvatation and acidity. Lewis acids and bases. Hard and soft bases and acids (HSBA). Applications of the HSBA principle to ambident nucleophiles. Effect of the structure on the acidity and basicity.
7.Nucleophilicity. Dipolar aprotic solvents. Ion pairs and nucleophilicity. Alpha effect. Nucleophilic catalysis.
8. Solvent effects on the reaction rate. Winstein-Grunwald equation. Y values. Solvatochromic functions
2.Non-kinetic methods. Stereochemical studies of the nucleophilic substitution of tetracordinated carbons. Stereochemical tools for the determination of the stereoselectivity of reactions. Crossover experiments. Isotopic labelling.
3.Substituent effects. Inductive (field) effects through bonds and through space. Stereoelectronic effects. Steric effects. Attractive van der Waals interactions.
4.Hammett equation. Applications of the Hammett equation to mechanistic studies. Rho values of two-step reactions. Nonlinearity of Hammett plots (minimum and maximum). Sigma, sigma(+) and sigma(-) values.
5.Steric effects of substituents. Es values.
6.Acid and bases.Kinetic and thermodynamic acidity. Solvatation and acidity. Lewis acids and bases. Hard and soft bases and acids (HSBA). Applications of the HSBA principle to ambident nucleophiles. Effect of the structure on the acidity and basicity.
7.Nucleophilicity. Dipolar aprotic solvents. Ion pairs and nucleophilicity. Alpha effect. Nucleophilic catalysis.
8. Solvent effects on the reaction rate. Winstein-Grunwald equation. Y values. Solvatochromic functions
- Teacher: Silvio Biali