Quantum Chemistry of Organic Compounds : Mechanisms of Reactions

Chemistry is the science of substances (today we would say molecules) and their transformations. Central to this science is the complexity of shape and function of its typical representatives. There lies, no longer dependent on its vitalistic antecedents, the rich realm of molecular possibility called organic chemistry. In this century we have learned how to determine the three-dimensional structure of molecules. Now chemistry as whole, and organic chemistry in particular, is poised to move to the exploration of its dynamic dimension, the busy business of transformations or reactions. Oh, it has been done all along, for what else is synthesis? What I mean is that the theoretical framework accom­ panying organic chemistry, long and fruitfully laboring on a quantum chemical understanding of structure, is now making the first tentative motions toward building an organic theory of reactivity. The Minkin, Simkin, Minyaev book takes us in that direction. It incorporates the lessons of frontier orbital theory and of Hartree-Fock SCF calculations; what chemical physicists have learned about trajectory calculations of selected reactions, and a simplified treatment of all-important solvent effects. It is written by professional, accomplished organic chemists for other organic chemists; it is consistently even-toned in its presentation of contending approaches. And very much up to date. That this contemporary work should emerge from a regional university in a country in which science has been highly centralized and organic chemistry not very modern, invites reflection. This textbook on the application of ab initio and semiempirical techniques for the analysis of organic reaction mechanisms is designed for chemistry undergraduates. The material is presented according to the mechanistic types: nucleophilic and electrophilic substitution, addition reactions, radical, pericyclic, proton and electron transfer reactions. Orbital and electrostatic models are used for structural correlations of interacting molecular systems along the reaction paths. Particular attention is focussed on the characteristics of the transition state. The text combines phenomenology with the basic theoretical principles needed to understand and predict chemical reactivity. This textbook on the application of ab initio and semiempirical techniques for the analysis of organic reaction mechanisms was written for chemistry undergraduates. The material is presented according to the mechanistic types: nucleophilic and electrophilic substitution, addition reactions, radical, pericyclic, proton and electron transfer reactions. Orbital and electrostatic models are used for structural correlations of interacting molecular systems along the reaction paths. Particular attention is focused on the characteristics of the transition state. The text combines phenomenology with the basic theoretical principles needed to understand and predict chemical reactivity Front Matter....Pages I-XV Potential Energy Surfaces of Chemical Reactions....Pages 1-60 Quantum Chemical Methods for Calculating Potential Energy Surfaces....Pages 61-87 Effects of the Medium....Pages 88-105 Orbital Interactions and the Pathway of a Chemical Reaction....Pages 106-115 Substitution Reactions....Pages 116-169 Addition Reactions....Pages 170-180 Low-Energy Barrier Reactions. Structural Modelling....Pages 181-189 Radical Reactions....Pages 190-209 Electron and Proton Transfer Reactions....Pages 210-237 Pericyclic Reactions....Pages 238-263 Back Matter....Pages 265-270