| preface . 1 the transition state 1.1 mechanism as a progression of states 1.2 structure and its interpretation 1.3 interconversion of states-reaction and encounter complexes 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 ofleast 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 intennediates 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 intennediates 3 the effect of changes in reactant structure 3.1 introduction 3.2 comparison of known with unknown-the leffler approach 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-state structures? 7 bio-organic group transfer reactions 7.1 relative timing of bond formation and bond fission 7.2 acyl group transfer 8 catalvsis 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 ofproton 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 reaction mechanisms a.2 supplementary tables a.2 estimation of ionization constants a.4 estimation of partition coefficients a.5 fitting data to theoretical equations references index ... |
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