Advances in Physical Organic Chemistry, Volume 39 (Advances in Physical Organic Chemistry)

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. Editor's preface.pdf 1 Editor’s preface 1 Contents.pdf 3 Contents 3 Isotope effects and quantum tunneling in enzyme-catalyzed hydrogen transfer. Part I. The experimental basis.pdf 5 Isotope effects and quantum tunneling in enzyme-catalyzed hydrogen transfer. Part I. The experimental basis 5 Introduction 6 Quantum tunneling in chemical reactions 6 Quantum tunneling in solution reactions 7 Data reduction for isotope-effect temperature dependences 10 A simplified account of the Bell tunneling model 11 Traditionally expected features of hydrogen isotope effects 14 QUANTUM TUNNELING IN ENZYME-CATALYZED REACTIONS: BREAKTHROUGHS 20 The expression of intrinsic isotope effects in multistep reactions 22 Klinman’s approach to kinetic complexity 24 Experimental phenomenology of quantum tunneling in enzyme-catalyzed reactions 26 Hydride-transfer reactions involving nicotinamide cofactors 26 Northrop’s method for intrinsic isotope effects 33 Commitments 6 Huskey’s rules for violations of the rule of the geometric mean and the Swain-Schaad relationships 41 Hydride-transfer reactions involving other cofactors 42 Hydrogen-atom transfer reactions 45 Proton-transfer reactions 47 Experimental signatures of tunneling 48 Observations that do not definitively indicate tunneling 48 Observations that likely indicate tunneling 49 Models for tunneling in enzyme reactions 50 Bell tunneling 50 Tunneling assisted by protein motion 50 Tunneling as a contribution to catalysis: prospects and problems 51 References 52 One- and two-electron oxidations and reductions of organoselenium and organotellurium compounds.pdf 56 One- and two-electron oxidations and reductions of organoselenium and organotellurium compounds 56 Introduction 56 Two-electron oxidations and reductions of selenium and tellurium compounds 57 Diorganochalcogenides and diorganochalcogen(IV) dihalides 57 Dehalogenation of vicinal-organic dihalides 68 Halogenation of organic substrates with chalcogen(IV) dihalides 74 Organochalcogen(II) and organochalcogen(IV) compounds with an odd number of ligands 77 Oxidation of thiols and related compounds with organoselenium(IV) and organotellurium(IV) compounds 79 Other oxidations with selenoxides and telluroxides 83 Thiolperoxidase and haloperoxidase-like activity of organoselenides and organotellurides 85 Electrochemical reduction of diorganotellurium(IV) species 90 One-electron oxidation of selenium and tellurium compounds 94 Diarylselenides and tellurides 95 Alkylarylselenides and tellurides 103 Dialkylselenides and tellurides 108 Heterocyclic selenides and tellurides: selected examples 114 Antioxidant activity in functional assays 115 References 117 Chiral clusters in the gas phase.pdf 123 Chiral clusters in the gas phase 123 Introduction 123 Ionic and molecular clusters in the gas phase 125 Characterization and classification of non-covalent intracomplex interactions 126 Noncovalent interactions in supramolecular systems 128 Noncovalent interactions in life sciences 128 Metal ions in biological systems 129 Chiral clusters 130 Experimental methodologies 131 Cluster sources 132 Neutral clusters from supersonic beam 133 Spectroscopy of neutral clusters 134 Sources of ionic clusters 143 Mass spectrometry of ionic clusters 146 Ion-dipole complexes in dense gases: the radiolytic approach 154 Chiral recognition in molecular clusters 154 Structure of molecular complexes 155 Energetics of molecular complexes 168 Chiral effects in rydberg electron-bound complexes 170 Chiral recognition in ionic clusters 172 Proton-bound complexes 172 Metal-bound complexes 180 Enantioselective self-assembling of amino acids 185 Host-guest inclusion complexes 189 Reactivity of chiral ion-dipole complexes 209 Concluding remarks 242 Acknowledgements 243 References 243 Dynamics for the reactions of ion pair intermediates of solvolysis.pdf 258 Dynamics for the reactions of ion pair intermediates of solvolysis 258 Introduction 258 A ‘‘Global’’ scheme for solvolysis 259 Clocks for reactions of ion pairs 260 Addition of solvent to carbocation-anion pairs 263 Protonation of a carbocation-anion pair 268 Isomerization of ion pair reaction intermediates 269 Reorganization of ion pairs in water 270 Internal return of isotopically labeled ion pairs 275 Racemization of ion pairs 279 Concluding remarks 281 Acknowledgements 281 References 281 Subject Index.pdf 284 Subject Index 284 Author Index.pdf 293 Author Index 293 Cumulative Index of Authors.pdf 306 Cumulative Index of Authors 306 Cumulative Index of Titles.pdf 308 Cumulative Index of Titles 308 Content: Contents Pages v-vi Editor's preface Pages vii-viii Dynamics for the reactions of ion pair intermediates of solvolysis Review Article Pages 1-26 John P. Richard, Tina L. Amyes, Maria M. Toteva, Yutaka Tsuji Isotope effects and quantum tunneling in enzyme-catalyzed hydrogen transfer. Part I. The experimental basis Review Article Pages 27-77 Floyd E. Romesberg, Richard L. Schowen One- and two-electron oxidations and reductions of organoselenium and organotellurium compounds Review Article Pages 79-145 Michael R. Detty, Margaret E. Logan Chiral clusters in the gas phase Review Article Pages 147-281 Maurizio Speranza Author Index Pages 283-295 Cumulative Index of Authors Pages 297-298 Cumulative Index of Titles Pages 299-306 Subject Index Pages 307-315