Advanced physical organic chemistry. Methods for the elucidation of reaction mechanisms. Reactive intermediates. Thermochemistry; isotope labeling; cross-over experiments; kinetic isotope effects; thermodynamics-kinetics correlations; solvation and ion pairs; radical reactions; electron transfer; spectroscopic methods.
Objective
Methods for the elucidation of organic reaction mechanisms.
Content
Thermochemistry: homodesmic reactions, estimation with group increments. Non-kinetic methods: product analysis, labeling with stable isotopes, cross-over experiments. Kinetic methods: establishing intermediates, isotope effects. Thermodynamic-kinetic correlations: LFER, Marcus relation. Solvation and ion pairs.
Lecture notes
A printed script are handed out in the course. This material is also available for download from the web page of the course (as pdf files).
Literature
Additional reading and original publications are cited in the lectures.
Prerequisites / Notice
Required level: Courses in organic and physical chemistry of the first and second year. Each participant is expected to contribute to a 30 min. seminar (prepared by groups of 2-4 students), presented in the last weeks of the semester.