Advances in Physical Organic Chemistry /

Cover; ADVISORY BOARD; Advances inPhysical Organic Chemistry; Copyright Page; Contents; Editor's Preface; Contributors to Volume 44; Biographical Essay: A. Jerry Kresge; 1 Introduction; 2 Solvent deuterium isotope effects; 3 Br�nsted coefficients; 4 Generation of reactive intermediates by laser flashphotolysis; Acknowledgments; References; Chapter 1 The low-barrier hydrogen bond in enzymic catalysis; 1 Introduction; 2 Properties of hydrogen bonds; 3 Role of low-barrier hydrogen bonds in enzymatic reactions; 4 Conclusion; References; Chapter 2 Stabilities and Reactivities of Carbocations

1 Introduction2 Stabilities of carbocations; 3 Reactivity of carbocations; Acknowledgments; References; Chapter 3 Secondary equilibrium isotope effects on acidity; 1 Scope; 2 Theory; 3 Methodology; 4 Secondary deuterium isotope effects on acidities in solution; 5 Heavy-atom isotope effects on acidities; 6 Secondary isotope effects on Lewis acid-Lewis base interactions; 7 Secondary isotope effects on gas-phase acidity and basicity; 8 Secondary isotope effects on conformational equilibrium; 9 Secondary isotope effects on tautomeric equilibria; 10 Secondary isotope effects on hydrogen bonding

11 Secondary isotope effects in chromatography12 Secondary isotope effects on molecular structure; 13 Origin of secondary isotope effects on acidity; Acknowledgments; References; Chapter 4 Molecular dynamics simulations and mechanism of organic reactions: non-TST behaviors; 1 Introduction; 2 Nonstatistical product distribution; 3 Avoided intermediate on IRC; 4 Non-IRC reaction pathway; 5 Path bifurcation; 6 Reaction time course and product and energy distributions; 7 Nonstatistical barrier recrossing; 8 QM/MM-MD; 9 Full quantum MD simulation in water; 10 Summary and outlook; Acknowledgments

ReferencesChapter 5 The principle of nonperfect synchronization: recent developments; 1 Introduction; 2 Proton transfers in solution; 3 Proton transfers in the gas phase: ab initio calculations; 4 Other reactions; 5 Summary and concluding remarks; Acknowledgments; References; Chapter 6 Kinetic studies of keto-enol and other tautomeric equilibria by flash photolysis; 1 Introduction; 2 Methods; 3 Examples; 4 Rate-equilibrium relationships; 5 Conclusion and outlook; References; Chapter 7 The role of pre-association in Br�nsted acid-catalyzed decarboxylation and related processes

1 Catalysis and reversibility2 Catalysis of decarboxylation; 3 Decarboxylation, internal return, and directionality; 4 Pre-association; 5 Catalyzing thiamin diphosphate catalysis; 6 12C/13C kinetic isotope effects and pre-association catalysis; 7 Implications of blocking reversion for enzyme catalysis; 8 OMP decarboxylase - decarboxylation and protonation of orotidine monophosphate; 9 General trends in catalyzed decarboxylation; 10 Decarboxylation of aromatic carboxylic acids; 11 Decarboxylation of 3-ketoacids; 12 Conclusions; References; AUTHOR INDEX; Cumulative Index of Authors

Cumulative Index of Titles

Advances in Physical Organic Chemistry provides the chemical community with authoritative and critical assessments of the many aspects of physical organic chemistry. The field is a rapidly developing one, with results and methodologies finding application from biology to solid state physics.* Reviews the application of quantitative and mathematical methods towards understanding chemical problems * Multidisciplinary volumes cover organic, organometallic, bioorganic, enzymes and materials topics