Quantum Chemistry of Organic Compounds: Mechanisms of Reactions

Quantum Chemistry of Organic Compounds: Mechanisms of Reactions

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By (author) V. I. Minkin, By (author) Boris Ya. Simkin, By (author) Ruslan M. Minyaev

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  • Publisher: Springer-Verlag Berlin and Heidelberg GmbH & Co. K
  • Format: Paperback | 288 pages
  • Dimensions: 156mm x 234mm x 15mm | 440g
  • Publication date: 8 December 2011
  • Publication City/Country: Berlin
  • ISBN 10: 3642756816
  • ISBN 13: 9783642756818
  • Edition statement: Softcover reprint of the original 1st ed. 1990
  • Illustrations note: 35 black & white tables, biography

Product description

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.

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Table of contents

1 Potential Energy Surfaces of Chemical Reactions.- 1.1 Introduction. Mechanism of Chemical Reaction and Quantum Chemistry.- 1.2 Choice of a Coordinate System and the Representation of a PES.- 1.3 Topography of the PES and Properties of a Reacting System.- 1.3.1 Critical Points.- 1.3.2 The Regions of the Minima on the PES.- 1.3.2.1 Vibrational Spectrum of Molecules.- 1.3.2.2 Calculation of Thermodynamic Functions of Molecules.- 1.3.2.3 Topological Definition of Molecular Structure.- 1.3.2.4 Structural Diagrams.- 1.3.3 Saddle Points on the PES. Transition States.- 1.3.3.1 Localization of the Transition States on the PES.- 1.3.3.2 Symmetry Selection Rules for Transition State Structures.- 1.3.3.3 Calculation of Activation Parameters of Reactions and of Kinetic Isotopic Effects.- 1.3.4 Pathway of a Chemical Reaction.- 1.3.4.1 Ambiguity of the Definition.- 1.3.4.2 A More Accurate Definition of the MERP and the Reaction Coordinate.- 1.3.4.3 Symmetry Demands on the Reaction Path.- 1.3.4.4 Chiral and Achiral Pathways of Degenerate Reactions.- 1.3.5 Empirical Correlations of the Reaction Pathways.- 1.3.5.1 Molecular Vibrations and the Reaction Coordinate.- 1.3.5.2 The Principle of Least-Motion.- 1.3.5.3 Structural Correlations of the Pathways of Chemical Reactions.- 1.4 Dynamic Approach.- 1.5 Tunnelling Effects in Chemical Reactions.- 1.6 Description of Nonadiabatic Reactions.- References.- 2 Quantum Chemical Methods for Calculating Potential Energy Surfaces.- 2.1 General Requirements upon the Methods for Calculating Potential Energy Surfaces.- 2.2 Nonempirical (ab initio) Methods. The Hartree-Fock Method.- 2.2.1 Closed Electron Shells.- 2.2.2 Open Electron Shells.- 2.2.3 Basis Sets of Atomic Orbitals.- 2.2.4 Electron Correlation.- 2.2.5 The Problem of Stability of Hartree-Fock Solutions.- 2.3 Semiempirical Methods.- 2.3.1 The Extended Huckel Method.- 2.3.2 Semiempirical Selfconsistent Field Methods.- 2.3.2.1 The CNDO/2 Method.- 2.3.2.2 The MINDO/3 Method.- 2.3.2.3 The MNDO Method.- 2.3.2.4 The AM1 Method.- References.- 3 Effects of the Medium.- 3.1 A General Scheme for Calculating the Solvation Effects.- 3.2 Macroscopic Approximation.- 3.2.1 General Theory.- 3.2.2 Model Hamiltonians in the Macroscopic Approximation.- 3.2.2.1 Model Hamiltonian in the Kirkwood Approximation.- 3.2.2.2 A Model Hamiltonian Based on the Born Formula. Scheme of Solvatons.- 3.2.2.3 The Scheme of Virtual Charges.- 3.2.2.4 The Theory of Selfconsistent Reactive Field.- 3.3 Discrete Representation of Solvent Molecules. Model Hamiltonians in the Microscopic Approximation.- 3.4 Specific Features of the Supermolecular Approach in Studies of Solvation Effects.- 3.5 Statistical Methods for Studying Solutions.- References.- 4 Orbital Interactions and the Pathway of a Chemical Reaction.- 4.1 The Role of Frontier Orbitals.- 4.2 Theory of Orbital Interactions.- 4.3 Components of the Interaction Energy of a Reacting System in a Transition State.- 4.4 Isolobal Analogy.- References.- 5 Substitution Reaction.- 5.1 Nucleophilic Substitution at a Tetrahedral Carbon Atom.- 5.1.1 The SN2 Reactions.- 5.1.1.1 Stereochemistry of the Reactions.- 5.1.1.2 Reaction Coordinate and the Structure of the Transition State.- 5.1.1.3 Energetics and Stoichiometric Mechanism of the Gas-Phase SN2 Reactions.- 5.1.1.4 Effect of the Solvent.- 5.1.1.5 Reactions with Retention of Configuration of the Carbon Atom.- 5.1.2 The SN1 Reactions.- 5.2 Electrophilic Substitution at the Tetrahedral Carbon Atom.- 5.3 Nucleophilic Substitution at the Carbon Atom of the Carbonyl Group.- 5.3.1 The Stoichiometric Mechanism.- 5.3.2 Homogeneous Catalysis.- 5.3.3 Stereochemistry of the Reaction.- 5.3.3.1 The Direction of Nucleophilic Attack and Orbital Steering.- 5.3.3.2 Stereochemical Control of the Breakdown of the Tetrahedral Adduct.- 5.4 Aromatic Electrophilic Substitution Reactions.- 5.5 Nucleophilic Substitution at the Nitrogen, Phosphorus, and Sulfur Centers.- 5.5.1 Substitution at the Nitrogen Atom of Nitroso- and Nitro-Groups.- 5.5.2 Substitution at the Dicoordinate Sulfur Atom.- 5.5.3 Substitution at Tricoordinate Sulfur and Phosphorus Centers.- 5.5.4 Substitution at Tetracoordinate Phosphorus.- 5.5.5 Substitution at Pentacoordinate Phosphorus.- 5.5.6 Inclusion of the Polytopal Rearrangements of Intermediates in the Overall Reaction Scheme.- References.- 6 Addition Reactions.- 6.1 Electrophilic Additions to Multiple Bonds.- 6.2 Nucleophilic Addition to Alkenes.- 6.3 Nucleophilic Addition to a Triple Bond.- References.- 7 Low-Energy Barrier Reactions. Structural Modelling.- 7.1 The Principle of Correspondence Between Structures of the Initial and the Transition State of Reaction.- 7.2 Nucleophilic Rearrangements and Tautomerizations.- 7.3 Cyclization Reactions.- 7.4 Topochemical Reactions.- References.- 8 Radical Reactions.- 8.1 Specific Features of the Theoretical Analysis of Radical Reactions.- 8.2 Free-Radical Reactions.- 8.2.1 Bond-Cleavage and Addition Reactions.- 8.2.2 Radical Substitution Reactions at the Tetrahedral Carbon Atom.- 8.3 Reactions with Formation of Biradicals.- 8.4 The Reactions of Carbenes.- 8.4.1 Addition to the Double Carbon-Carbon Bond.- 8.4.2 Insertion into ?-Bonds.- References.- 9 Electron and Proton Transfer Reactions.- 9.1 Electron Transfer Reactions.- 9.1.1 Single Electron Transfer Reactions in Organic Chemistry.- 9.1.2 Elementary Act of Electron Transfer.- 9.1.3 Theoretical Studies of the Mechanism of SRN1 Reactions.- 9.2 Proton Transfer Reactions.- 9.2.1 Potential Energy Curves and Activation Barriers.- 9.2.2 Stereochemistry.- 9.2.3 Proton Transfer in Systems with the Intramolecular Hydrogen Bonding.- 9.2.4 The Tunnelling Mechanism in Proton Transfer Reactions.- 9.2.5 Double Proton Migrations.- References.- 10 Pericyclic Reactions.- 10.1 Reactions of Cycloaddition.- 10.1.1 [2 + 2]-Cycloaddition.- 10.1.2 [4 + 2]-Cycloaddition.- 10.2 Electrocyclic Reactions.- 10.3 Sigmatropic Rearrangements.- 10.4 Haptotropic Rearrangements.- 10.5 Ion-Radical Pericyclic Reactions.- References.- List of Abbreviations.