Symmetry, Spectroscopy, and Crystallography

Written in a clear and understandable manner, this book provides a comprehensive, yet non-mathematical, treatment of the topic, covering the basic principles of symmetry and the important spectroscopic techniques used to probe molecular structure. The chapters are extensively illustrated and deal with such topics as symmetry elements, operations and descriptors, symmetry guidelines, high-fidelity pseudosymmetry, crystallographic symmetry, molecular gears, and experimental techniques, including X-ray crystallography and NMR spectroscopy. As an additional feature, 3D animations of most of the structures and molecules covered are available online at wiley.com. As a result, chemists learn how to understand and predict molecular structures and reactivity. Authored by a renowned expert with numerous publications and an excellent track record in research and teaching, this is a useful source for graduate students and researchers working in the field of organic synthesis, physical chemistry, biochemistry, and crystallography, while equally serving as supplementary reading for courses on stereochemistry, organic synthesis, or crystallography.

Auteur
Robert Glaser is Emeritus Professor of Chemistry at Ben-Gurion University of the Negev, Beer-Sheva, Israel. He also holds an appointment as Visiting Professor in the Cross-Border Program in Biological Chemistry Budejoice (Budaweis), Czech Republic, administered by the University of South Bohemia/Universität Johannes Kepler in Linz, Austria. He also teaches at the Feinberg Graduate School of the Weizmann Institute of Science in Rehovot, Israel. Robert Glaser received his BA in chemistry at the University of Pennsylvania (USA) in 1963. Upon graduation he worked as a development chemist in the Structural Adhesives Division of the Pittsburg Plate Glass Company. Concurrently, he undertook part-time MSc studies in polymer chemistry at the Polytechnic Institute of Brooklyn, USA. After three years he began full-time studies, graduating Rutgers State University, USA, in 1969. From 1969 - 1971 he spent a two-year postdoctoral fellowship at Princeton University (USA) under guidance of Prof. P. von Rague Schleyer and Prof. R. Landgridge. After immigrating to Israel in 1971, he built up a new Department of Chemistry at the recently established University of the Negev in Beer-Sheva, where he became full professor in 1997. He has authored over 100 publications on the topic of organic and inorganic stereochemistry, molecular modeling, computer assisted drug design, and structure determination via NMR spectroscopic techniques.

Texte du rabat

This book aims to show the common interface between the aesthetic world of form and that of structural chemistry. Written in a clear and understandable manner, it provides a comprehensive, yet non-mathematical, treatment of the topic, covering the basic principles of symmetry and the important spectroscopic techniques used to probe molecular structure.

The chapters are extensively illustrated and deal with such topics as symmetry elements, operations and descriptors, symmetry guidelines, high-fidelity pseudosymmetry, crystallographic symmetry, molecular gears, and experimental techniques, including X-ray crystallography and NMR spectroscopy. As a result, chemists learn how to understand and predict molecular structures and reactivity.

Authored by a renowned expert with numerous publications and an excellent track record in research and teaching, this is a useful source for graduate students and researchers working in the field of organic synthesis, physical chemistry, biochemistry, and crystallography, while equally serving as supplementary reading for courses on stereochemistry, organic synthesis, or crystallography.

3D animations showing most of the molecules contained in this book can be found under www.wiley.com/go/Glaser/Symmetry

Contenu

From the Author's Desk XIII

1 Symmetry/Pseudosymmetry: Chirality in Molecules, in Nature, and in the Cosmos 1

1.1 Introduction 1

1.2 Rudimentary GroupTheory, Isometry, and Symmetry 4

1.3 Asymmetric versus Chiral: The I-Symmetry of Viral Capsids 7

1.4 The Birth of Chirality as a Chemical Concept 9

1.5 Apparent Symmetry (High-Fidelity Pseudosymmetry) and the Quantification of Distortion from the Ideal 11

1.6 Chirality in Form and Architecture: Symmetry versus Broken Symmetry 16

1.7 Chirality in Nature: Tropical Storms, Gastropods (Shells), and Fish 17

1.8 Extraterrestrial Macroscale Chirality: Spiral Galaxies, Martian Sand Devils, Jovian Great Red Spot, Neptune's Great Dark Spot, and Venusian South-Pole Cloud Vortex 20

1.9 Analyses of Amino Acid Chirality in Extraterrestrial Samples with GasLiquid Chromatography Chiral Columns 23

2 Enantiospecificity of Pheromones, Sweeteners, Fragrances, and Drugs 25

2.1 Enantiospecificity of Pheromones, Sweeteners, and Fragrances 25

2.2 The Importance of Chirality in Drug Therapy 27

3 Bonding Parameters and the Effect of Local Environment on Molecular Structure 33

3.1 Symmetry Arguments and the Effect of the Environment on Molecular Structure 33

3.2 The Effect of Local Environment on Molecular Models and Molecular Structure 34

3.3 Torsion Angles and Molecular Conformation 35

3.4 Symmetry Considerations of Atomic Orbital Hybridization and Bonding Parameters 39

4 Historical Development of Structural Chemistry: From Alchemy to Modern Structural Theory 41

4.1 Hemihedralism in Quartz Crystals: Setting the Stage for the Birth of Stereochemistry 41

4.2 Tartaric Acid and Alchemy 45

4.3 Hemihedralism in Crystalline Tartaric Acid Salts: The Birth of Molecular Chirality 46

4.4 Gift for Prelog's Retirement: A Matched Pair of u,x-Hemihedral Faced Right- and Left-Handed Quartz Crystals 54

4.5 Early Structural Representations of Organic Substances and the Development of Modern Structural Concepts 55

4.6 Fischer Projections to Determine - and -Anomeric Configurations 64

5 Chiroptical Properties 67

5.1 The Language of Symmetry, Isomerism, and the Characterization of Symmetry Relationships within and between Molecules 67

5.2 Chiroptical Properties: Circular Birefringence, Optical Rotatory Dispersion, and Circular Dichroism 68

5.3 Miller Indices and Fractional Coordinates in Crystallography 74

5.4 Scanning Tunneling Microscopy 78

5.5 Direct Visualization of an Enantiomer's Absolute Configuration in the Gas Phase 82

6 Symmetry Comparison of Molecular Subunits: Symmetry in Nuclear Magnetic Resonance Spectroscopy and in Dynamic NMR 85

6.1 Symmetry in NMR Spectroscopy 85

6.2 Symmetry Comparison of Molecular Subunits, Topicity Relationships 87

6.3 Dynamic Stereochemistry, Dynamic Nuclear Magnetic Resonance Spectroscopy (DNMR) 90

6.4 Use of Permutations in DNMR for Topomerization-, Enantiomerization-, and Diastereomerization-Exchange Processes 92

7 Prochirality, Asymmetric Hydrogenation Reactions, and the CurtinHammett Principle 99

7.1 Prochirality of Enantiotopic Subunits 99

7.2 Homogeneous Hydrogenation by RhodiumI/Achiral Diphosphine Catalysts Differentiates the Diastereotopic Prochiral Faces of Olefins 101

7.3 Homogeneous Hydrogenation by RhodiumI/(Chiral Diphosphine) Catalysts Differentiates the Enantiotopic Prochiral Faces of Olefins: The CurtinHammett Principle 104

8 Stereogenic Elements, Chirotopicity, Permutational Isomers, and Gear-Like CorrelatedMotion of Molecular Subunits 113

8.1 Stereogenicity, Stereogenic Elements, Chirotopicity, and the Ambiguity of Some Stereochemical Terms 113

8.2 Triarylamine Propellers 115

8.3 Dynamic Stereochemistry of Permutational Isomers: Correlated Motion in Triarylamines 116

8.4 Relative Stereochemical Descriptors: Retro-Inverso Isomers 122

**9 Symmetry in Extended Periodic Arrays of Molecular Crystals and the Relevance of Penrose Tiling Rules for Nonperiodic Quasicrystal Packing 12…