1THE TRANSITION STATE

1.1 Mechanism as a progression of states

1.2 Structure and its interpretation

1.3 Interconversion of states—reaction and encountercomplexes

1.4 Methods of representing reaction mechanisms

1.5 General considerations concerning reaction mechanisms

1.6 Energy transfer, redistribution and relaxation

1.7 Stereoelectronic effects

1.8 Principle of non-perfect synchronization

1.9 Principle of least nuclear motion

1.10 Is the transition state a molecule?

2 KINETICS AND MECHANISM

2.1 Introduction

2.2 Kinetic method

2.3 Rate law and mechanism

2.4 Steady state and non-steady state

2.5 Rate-limiting step

2.6 Curtin-Hammett principle

2.7 Which transition state is being observed kinetically?

2.8 Demonstration of intermediates by kinetics

2.9 Change in mechanism

2.10 Rules for change in mechanism or rate-limiting step

2.11 Trapping of intermediates

2.12 Composition of the transition state of the rate-limiting step

2.13 Kinetic ambiguities

2.14 Microscopic reversibility

2.15 Kinetic and thermodynamic control

2.16 Isotope labelling techniques and detection of intermediates

3 THE EFFECT OF CHANGES IN REACTANT STRUCTURE

3.1 Introduction

3.2 Comparison of known with unknown—the Lefflerapproach

3.3 Polar and steric substituent effects

3.4 Hammett's equation

3.5 Bronsted's equation

3.6 Transition-state acidity and transition-state complexation

3.7 Topology of transition states

4 KINETIC AND EQUILIBRIUM ISOTOPE EFFECTS

4.1 Origin of isotope effects

4.2 Measurement of kinetic isotope effects

4.3 Primary isotope effects

4.4 Solvent isotope effects

4.5 Heavy-atom isotope effects

4.6 Secondary isotope effects and transition-state structure

5 TRANSITION STATES FROM EXTERNAL EFFECTS

5.1 Introduction

5.2 Solvent effects

5.3 Reactions in strongly acidic and strongly basic media

5.4 Solvent ionizing power

5.5 Variation of pressure and temperature

6 TRANSITION STATE STRUCTURES-ANOMALIES

6.1 Introduction

6.2 Reactivity-selectivity relationship

6.3 Microscopic medium effects

6.4 Curvature in free-energy relationships

6.5 Bronsted anomalies

6.6 Do experimental parameters directly measure transition-statestructures?

7 BIO-ORGANIC GROUP TRANSFER REACTIONS

7.1 Relative timing of bond formation and bond fission

7.2 Acyl group transfer

8 CATALYSIS

8.1 Reactivity

8.2 Coenzymes

8.3 Proton transfer

8.4 Metal ions

8.5 Intramolecular reactions

9 COMPLEXATION CATALYSIS

9.1 General considerations

9.2 Covalent catalysis

9.3 Inclusion complexation

9.4 Catalysis by organized aggregates and phases

9.5 Future directions

10 SOME ENZYMES

10.1 Introduction

10.2 Enzymes catalysing acyl group transfer

10.3 Catalysis of proton transfer reactions

10.4 Carbon-carbon bond formation and fission

10.5 Transfer of the hydride ion

10.6 Alkyl group transfer

APPENDICES

A.1 IUPAC system for symbolic representation of reactionmechanisms

A.2 Supplementary tables

A.3 Estimation of ionization constants

A.4 Estimation of partition coefficients

A.5 Fitting data to theoretical equations

REFERENCES

INDEX