Theory Of Orientation And Stereoselection

Many organic chemists will agree with me that the old "electronic theory" has for a long time been inadequate for the interpretation of various new findings in chemistry, particularly for those of reactivity. Considering the outstanding progress which has been made during the past 20 years in the interpretation of these facts, aided by the molecular orbital theory, the time has finally come for a new book showing what is within and what is beyond the reach of quantum-chemical methods. It was therefore highly suitable that Dr. F. L. Boschke of the Springer Verlag suggested to me to make a contribution to a volume in the series "Topics in Current Chemistry" in February 1969. The article was published as Vol. 15, No 1 in June 1970. This new book is an expanded version of the article written in 1970. In this present volume several of the most up-to-date findings which have been gained in organic chemistry since then have been added. It is highly probable that a certain "theoretical" design in the experimenta lists' mind may have been the reason for these developments, whether they themselves are aware of it or not. Theory produces new experimental ideas and conversely, a host of experimental data add another vista to new theories. Due to the mutual beneficial effect of theory and experiment this book will always retain its value, although the quantum-chemical approach to the theory of reactivity is, of course, still in the develop mental stage.

First published in 1979 as the second edition of a 1972 original, this textbook provides a systematic account of an important area of organic chemistry - that of cycloadditions and molecular rearrangements. The necessary theoretical background for understanding these reactions is presented in non-mathematical form and various alternative approaches to the theory are compared. The core of the book is a descriptive account of various types of cycloaddition and rearrangement reactions. The synthetic importance of these reactions is emphasised and, by providing the mechanistic background, the book demonstrates to the reader the relationship between the different types of reactions. This book will be of value to anyone with an interest in organic chemistry.

A collection of selected papers on the Frontier Orbital Theory, with introductory notes. It provides the basic concept and formulation of the theory, and the physical and chemical significance of the frontier orbital interactions in chemistry, together with many practical applications. The formulation of the Intrinsic Reaction Coordinate and applications to some simple systems are also presented. The aim of this volume is to show by what forces chemical reactions are driven and to demonstrate how the regio- and stereo-selectivities are determined in chemical reactions. Students and senior investigators will gain insight into the nature of chemical reactions and find out how quantum chemical calculations are connected with chemical intuition.

Charge Sensitivity Analysis (CSA) represents a linear response treatment of molecular systems, based upon the chemical potential and hardness/softness concepts established within density functional theory (DFT). Recently, it has been shown to provide an attractive framework leading to novel approaches to chemical reactivity of open systems. The monograph presents the conceptual and methodological basis of the CSA covering its DFT roots, alternative resolutions and representations, sensitivities of closed and open atomic and molecular systems, charge stability criteria and relaxational effects due to the system environment, and alternative collective modes of charge redistribution. The CSA interaction energy in donor-acceptor systems is investigated in the second-order approximation. In particular, the relaxational contributions to the chemical potential, hardness and softness quantities are examined and their physical implications are summarized. The charge sensitivity concepts for reactive systems include: one- and two-reactant reactivity criteria, mapping relations between equilibrium displacements in the electron population and nuclear position spaces, the intersecting state model of charge transfer processes, intermediate hardness decoupling modes and the minimum energy coordinates, all defined in the electron population space. The conceptual developments are illustrated using recent qualitative and quantitative results on selected molecules, catalytic clusters and chemisorption systems. The CSA description is shown to connect directly to intuitive concepts and rules of chemistry, e.g., those related to interactions between hard/soft acids and bases.

In additionto covering thoroughly the core areas of physical organic chemistry -structure and mechanism - this book will escortthe practitioner of organic chemistry into a field that has been thoroughlyupdated.

This is the perfect complement to "Chemical Bonding - Across the Periodic Table" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community. The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemical models and faster computers.