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2016 | Book

The Chemical Bond: Lewis and Kossel’s Landmark Contribution Read chapter Read first chapter

The Chemical Bond I

100 Years Old and Getting Stronger

Editor: D. Michael P. Mingos

Publisher: Springer International Publishing

Book Series : Structure and Bonding

Part of: Springer Professional "Wirtschaft+Technik" , Springer Professional "Technik" , Springer Professional "Wirtschaft"

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About this book

The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant.
The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed.
Review articles for the individual volumes are invited by the volume editors

Table of Contents

Frontmatter
The Chemical Bond: Lewis and Kossel’s Landmark Contribution
Abstract
The seminal papers of Lewis and Kossel in 1916 are put into a historical perspective. Mendeleev’s periodic table, Thompson’s discovery of the electron, Ramsay and Raleigh’s discovery of the noble gases, Rutherford’s model of the atom and Bohr’s description of the stationary orbitals for the electrons in atoms all paid an important role in providing the background for Lewis and Kossel’s proposal that the chemical bond originated either from the transfer of electrons or the sharing of electron pairs. These insights depended on the attainment of inert gas configurations by the atoms either directly by electron transfer or electron-pair sharing. The model incorporated an evolutionary gene which has enabled it to survive and grow by incorporating subsequent developments in quantum physics. The simplicity of the model has resulted in the development of a notation, which is universally used by chemists and has evolved to plot the course of chemical reactions and predict their regioselectivities. Its initial limitations are discussed, and the way in which they have been overcome by an orbitally based model is recounted. The model has been repeatedly enriched by quantum mechanically based theoretical studies.
D. Michael P. Mingos
Charge Density and Chemical Bonding
Abstract
In the past 100 years, the Lewis diagram has frequently been challenged, modified, extended and rejected as being too simplistic. Those who teach chemistry to freshman, however, appreciate the diagram as one of the didactical rocks in the wild sea of ever developing science, because it is simple, easy to understand and long ranged in mediate basic chemistry. This article is aimed at the evaluation of the Lewis diagram in the light of modern charge density investigations and the topological analysis based on the quantum theory of atoms in molecules. Some old molecules like boranes, sulfate, and high-coordinate silicon will be revisited as well as some recent low-valent silicon species that were regarded impossible to make only some years ago. Can the Lewis diagram cope with new results from experiment and theory and be extended to “impossible” molecules? The answer is yes and that makes a model a good model: easy to adapt by and by and not suggesting any scientific dead ends, because the model might eventually be mistaken to be real from the inexperienced applicant.
Dietmar Stalke
Lewis Description of Bonding in Transition Metal Complexes
Abstract
Transition metal complexes have been playing an increasingly important role in modern chemistry in the past century, and this is partly due to their distinctive structure and bonding features that allow them to play a special role in organometallic reactions. Despite their importance, the current understanding of their structure and bonding relies to a large extent on sophisticated quantum chemical treatments, which do not encourage the formulation of more generalized rules. In this review, commemorating the centennial anniversary of the seminal Lewis paper, we would like to go back to basics and start from the classical Lewis description and then combine some observations we obtain from modern molecular orbital theory to give a simple but general bonding picture for transition metal complexes. This model, albeit simple, provides a localized description to metal–ligand interactions in these complexes and allows us to easily treat various cases with atypical metal–ligand or even metal–metal interactions in a modular manner.
Fu Kit Sheong, Wen-Jie Chen, Zhenyang Lin
Gilbert Lewis and the Model of Dative Bonding
Abstract
The electron-pair bonding model that was introduced by Gilbert Lewis 100 years ago is discussed in the light of modern quantum chemical methods for analysing the electronic structures of some simple molecules. It is argued that Lewis structures in conjunction with accurate quantum chemical calculations are still very useful for the description of chemical bonding. The emphasis lies on the difference between electron-sharing bonds A–B and dative bonds A → B which were suggested by Lewis as a general definition for acids and bases. The electron-pair model, if combined with quantum chemical calculations, remains a powerful guide for the search of new molecules and for understanding molecular structures.
Gernot Frenking, Markus Hermann
Structure and Bonding Patterns in Large Molecular Ligated Metal Clusters
Abstract
Although there will always be an Edisonian component to a search for new cluster compounds, the greater the understanding of the underlying chemistry, the more focused and efficient the search. It is why the rapid expansion of the synthesis and characterization of ligated transition-metal clusters over the last decades has been accompanied by theories about their bonding and electronic properties with the aid of conceptual ideas and theoretical models such as the development of electron-counting rules which govern the relationship between the structure and the electron count. This review summarizes these theoretical models, their historical development, their limits, and using a selection of specific examples among the extensive panoply of large ligated metal clusters available in the literature, shows how they can help in understanding their structural and electronic properties.
Jean-Yves Saillard, Jean-François Halet
Electronic Properties of Endohedral Clusters of Group 14
Abstract
The concept of stable “superatoms,” molecular species which mimic the shell closures emphasised by Lewis and Kossel, has become an important paradigm of stability in cluster chemistry. In this review we discuss recent work, both experimental and theoretical, on the family of endohedral clusters M@Ex, where M is a transition metal ion and E is a member of group 14 (Si, Ge, Sn, Pb). The structural chemistry within this family is very varied, ranging from deltahedral motifs for the heavier tetrels to open 3-connected structures such as the hexagonal prism in Cr@Si12. We explore the arguments that have been presented to rationalise these structural trends and their implications for chemical bonding.
Vaida Arcisauskaite, Xiao Jin, José M. Goicoechea, John E. McGrady
The Rich Structural Chemistry Displayed by the Carbon Monoxide as a Ligand to Metal Complexes
Abstract
The diatomic CO molecule is a very important ligand in organometallic chemistry. The bond between the carbonyl and a metal is moderately strong and consists of a sigma bond, formed by donation of electron density to the metal from the carbonyl’s highest occupied molecular orbital (HOMO, the 5σ), and π bonds, formed by donation of electron density from the metal to the carbonyl’s lowest unoccupied molecular orbital (LUMO, the 2π). The carbonyl may also serve as a bridging ligand connecting two or more metal atoms. Depending on the relative orientation between the carbonyl and metals, one may classify a bridging carbonyl as symmetric bridging, bent semibridging, linear semibridging, face bridging, and bridging isocarbonyls. The rich structural chemistry displayed arises from a complex interplay between the metal’s electronic structure and the carbonyl’s 5σ and 2π. In addition, the carbonyl’s occupied 1π and 4σ orbitals may in certain cases donate electrons when it binds to electron-deficient metals, further complicating the electronic structure. Such complexity in the carbonyl–metal interaction raises challenges to the simple applications of Lewis bonding ideas and electron counting rules. Therefore, theoretical analyses have been applied, largely in a case-by-case pattern, to investigate the rationales behind the CO’s rich structural chemistry.
Shengda Ding, Michael B. Hall
Backmatter
Metadata
Title
The Chemical Bond I
Editor
D. Michael P. Mingos
Copyright Year
2016
Electronic ISBN
978-3-319-33543-8
Print ISBN
978-3-319-33541-4
DOI
https://doi.org/10.1007/978-3-319-33543-8

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