Determination of Mechanism

Philosophy of mechanistic studies:

No reaction could be determined with 100% certainty.
One can only disproof a hypothetical mechanism, not
proof.
As the result, an approved, last mechanism is said to be
reasonable, not correct.
More than one method would be needed to confirm, and
their results must all be consistent.
Gather information from many experiments until enough
to induce or extrapolate to a general conclusion.
In the event that several hypotheses are found to fit the
facts, the simplest one is given preference.
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Determination of Mechanism
1
2

Identification of products
Determination of the
presence of intermediates

2.1 Isolation of intermediates

2.2 Detection of intermediates
2.3 Trapping of intermediates
2.4 Addition of a suspected
intermediate

Study of catalysis
3.1 General acid catalysis
3.2 Specific acid catalysis

Labeling study

4.1 Group labeling

4.2 Isotope labeling
4.3 Crossover experiments

Isomeric selectivity study

5.1 Regiochemical evidences
5.2 Stereochemical evidences

Kinetic studies
6.1 Measurement of rate
6.2 Mechanistic information
obtained from kinetic
studies
6.3 Rate law
6.4 Solvent effects

Kinetic isotope effects

7.1 Deuterium isotope effects

7.2 Primary isotope effects
7.3 Secondary isotope effects
7.4 Solvent isotope effects