Effects of electric fields on structure and reactivity : new horizons in chemistry / edited by Sason Shaik, Thijs Stuyver.

Print version record.

Electric-field-mediated chemistry is an emerging topic that is rapidly growing and fanning out in many directions. It involves theoretical and experimental aspects, as well as intense interplay between them, including breakthrough achievements such as the proof-of-principle that a Diels-Alder reaction, which involves two simultaneous C-C bond making events, can be catalysed or inhibited simply by changing the direction of an oriented external-electric field (OEEF). This productive interplay between the theoretical and experimental branches of chemistry is continuing, and gradually defining a new sub-field wherein various sources of electric fields, whether external or built-in and designed, or even surface induced fields (plasmons), are brought to bear on chemical reactions, molecular structures, and nano-systems, leading to control of reactivity, selectivity, chirality, molecular orientations, changes in structure, and in dynamics. Written by leaders in the field, Effects of Electric Fields on Structure and Reactivity is the first book on this exciting topic. Starting with an overview of the theory behind - and demonstrations of the effect of - electric fields on structure and reactivity, this accessible reference work aims to encourage those new to the field to consider harnessing these effects in their own work. Covering applications and recent theoretical developments, it is a useful resource for theoretical chemists and experimentalists alike.

Cover -- Effects of Electric Fields on Structure and Reactivity: New Horizons in Chemistry -- Preface -- Contents -- Chapter 1 -- Introduction to the Book -- 1.1 Introduction -- 1.1.1 The Chapters that Make this Book -- 1.1.2 Glossary of Electric Fields Types -- Abbreviations and Glossary of Terms -- References -- Chapter 2 -- The Impact of Electric Fields on Chemical Structure and Reactivity -- 2.1 Introduction -- 2.2 Atoms in External Electric Fields -- Removal of Forbidden- orbital Mixing -- 2.3 Bonds in External Electric Fields -- 2.3.1 Homonuclear Bonds in OEEFs: The MO Perspective

2.4.2 Examples of How Chemical Reactions Behave Under OEEFs -- 2.4.2.1 Diels-Alder Reactions in OEEF -- VBSCD Predictions -- 2.4.2.2 Diels-Alder Reactions in OEEF -- Computational Results -- 2.4.2.3 Diels-Alder Reactions in OEEF -- Mechanistic Crossover -- 2.4.3 Selectivity Controls of Diels-Alder Reactions by OEEFs Applied Off the Reaction- Axis -- 2.4.3.1 Y- OEEF Controls Exo/Endo Selectivity of Diels-Alder Reactions -- 2.4.3.2 X- OEEF Controls Chiral Discrimination in Diels-Alder Reactions -- 2.4.3.3 Summary of Global Controls of the Diels-Alder Reaction

2.4.4 Experimental/Theoretical Support for the Predicted OEEF Effects on the Diels-Alder Reaction -- 2.4.5 OEEF Effects in Other Reactions -- 2.4.5.1 OEEF- induced Regioselectivity During Bond Activation by a Model Active Species of Cytochrome P450 -- 2.4.5.2 Spin- state Selectivity in H- abstraction by Nonheme Complexes Under OEEFs -- 2.4.5.3 The Menshutkin Methyl Transfer Reaction Under OEEF -- 2.4.5.4 OEEF Acts as Tweezers that Fix the Orientation of Halogen Bonds and Stimulate Ionic Displacements by Nucleophilic Attack ...

2.4.5.5 Mechanistic and Rate Control in Oxidative Addition Reactions of Divalent Palladium (0) Complexes -- 2.5 Experimental Results Showing Product Selectivity Control by IEF and D- LEF -- 2.6 Dopamine Formation by CYP2D6 -- Directives and Dilemmas of the LEFs of Protein -- 2.7 OEEFs in the Presence of Solvents -- 2.7.1 The Menshutkin Reaction in Solvents -- 2.8 Summary -- Chemical Reactivity in the Presence of Electric Fields -- 2.9 Prospects -- Acknowledgements -- References -- Chapter 3 -- Experimentally Harnessing Electric Fields in Chemical Transformations -- 3.1 Introduction

Added to collection customer.56279.3