Introduction to Coordination Chemistry (eBook)

Paul V. Bernhardt, Geoffrey A. Lawrance (Autoren)

eBook Download: PDF

2024 | 2. Auflage
402 Seiten
Wiley (Verlag)
978-1-394-19072-0 (ISBN)

Infos

INTRODUCTION TO COORDINATION CHEMISTRY

An accessible introduction to one of the primary fields of study in Inorganic Chemistry, revised to incorporate contemporary topics and applications

Written in a highly readable, descriptive, and accessible style, Introduction to Coordination Chemistry examines and explains the interaction between metals and molecules that bind as ligands and the consequences of this assembly process. The book describes the chemical and physical properties and behavior of these complex assemblies and their applications. The contents of this book tell a story, taking the reader from fundamentals, including metal ions, ligands, metal-ligand bonding, and structure, to key concepts, such as stability, synthesis and mechanisms, properties, and characterization. Subsequent chapters address applications involving metals in biology, medicine, and industrial chemistry.

Written by two highly qualified academics, this newly revised Second Edition of Introduction to Coordination Chemistry has been thoroughly updated to include full-color images throughout, as well as now including:

• Information on instrument-based experimental methods to reflect the increasing use of sophisticated, commercially available instruments in laboratory teaching
• An expansion of the chapter Metals in Biology showing key developments in the vast field of metalloproteins and metalloenzymes
• An updated description of polymetallic compounds and new discussions of metal-containing nanomolecules pertinent to advancements in nanotechnology
• An expanded discussion of organometallic compounds and catalysts and updating of Concept Keys to summarize key topics and further reading at the end of each chapter

Introduction to Coordination Chemistry is an ideal textbook resource for undergraduate inorganic chemistry students in their second or third year or at the intermediate level who have completed a general introductory chemistry course and are moving to a first specialist course in coordination chemistry.

INORGANIC CHEMISTRY ADVANCED TEXTBOOK

This series reflects the pivotal role of modern inorganic and physical chemistry in a whole range of emerging areas, such as materials chemistry, green chemistry and bioinorganic chemistry, as well as providing a solid grounding in established areas such as solid state chemistry, coordination chemistry, main group chemistry and physical inorganic chemistry.

PAUL V. BERNHARDT is a Professor of Chemistry in the School of Chemistry and Molecular Biosciences, University of Queensland, Australia. Professor Bernhardt is a former President of the Royal Australian Chemical Institute (2014-2016) and Chair of its Inorganic Chemistry Division (2007-2010).

GEOFFREY A. LAWRANCE is an Emeritus Professor of Chemistry in the College of Engineering, Science, and Environment at the University of Newcastle, Australia. Professor Lawrance has held academic and visiting positions at several national and European universities.

Inhalt

Cover 1
Title Page 5
Copyright 6
Contents 7
Preface 11
Acknowledgements 12
Preamble 13
About the Companion Website 17
Chapter 1 The Central Atom 19
1.1 Key Concepts in Coordination Chemistry 19
1.2 A Who's Who of Metal Ions 24
1.2.1 Common and Uncommon Metals 27
1.2.2 An Alternative Concept of Common Metals 28
1.3 Metals in Molecules 30
1.3.1 Metals in the Natural World 31
1.3.2 Metals in Contrived Environments 32
1.3.3 Natural or Made?to?Measure Complexes 34
1.4 The Road Ahead 34
Concept Keys 36
Further Reading 36
Chapter 2 Complexes 38
2.1 The Central Metal Ion 38
2.2 Metal–Ligand Assembly 40
2.2.1 The Coordinate Bond 40
2.2.2 The Foundation of Coordination Chemistry 40
2.2.3 Complex Shape 41
2.3 The Nature of Bonding in Metal Complexes 46
2.3.1 Orbital Symmetry 46
2.3.2 Introducing Crystal Field Theory – d?Electrons Versus Ligand Lone Pairs 49
2.3.3 Ligand Field Theory – Molecular Orbitals to the Rescue 53
2.3.4 d?Electronic Configurations and Magnetism 66
2.3.5 Coordination Geometries Beyond Octahedral and Tetrahedral 68
2.4 Metal–Ligand Bonding in Organometallic Chemistry – Beyond Classical Werner Complexes 70
2.4.1 & rmpi
2.4.2 Carbon Monoxide and the Carbonyl Ligand 72
2.4.3 The Metallocenes 74
2.4.4 The 18 and 16 Electron Rules 76
2.5 Coupling – Polymetallic Complexes 77
2.6 Complex Lifetimes and Complexation Consequences 78
Concept Keys 79
Further Reading 80
Chapter 3 Ligands 81
3.1 Membership: Being a Ligand 81
3.1.1 What Makes a Ligand? 81
3.1.2 Making Attachments – Coordination 83
3.1.3 Chelation by Didentate Ligands 85
3.1.4 Chelate Ring Size 89
3.1.5 Donor Group Variation 92
3.1.6 Denticity 93
3.2 Ligand Basicity 94
3.2.1 Basic Binders 94
3.2.2 Bridging Ligands 96
3.3 Making Choices 99
3.3.1 Selectivity 99
3.3.2 Preferences 99
3.4 Polydentate Ligands 102
3.4.1 Introducing Ligand Shape 103
3.5 Polynucleating Ligands 104
3.5.1 Dinucleating Ligands 104
3.5.2 Mixed?metal Complexation 106
3.5.3 Binding to Macromolecules 107
3.6 Nonclassical Ligands in Organometallic Chemistry 108
Concept Keys 111
Further Reading 112
Chapter 4 Shape 113
4.1 Getting in Shape 113
4.2 Coordination Number and Shape 116
4.2.1 One?Coordination (ML) 117
4.2.2 Two?Coordination (ML2) 117
4.2.3 Three?Coordination (ML3) 118
4.2.4 Four?Coordination (ML4) 120
4.2.5 Five?Coordination (ML5) 123
4.2.6 Six?Coordination (ML6) 126
4.2.7 Higher Coordination Numbers (ML7 to ML9) 128
4.3 Influencing Shape 132
4.3.1 Metal Ion Influences 132
4.3.2 Ligand Influences 134
4.3.3 Chameleon Complexes 135
4.4 Isomerism – Real 3D Effects 136
4.4.1 Introducing Stereoisomers 136
4.4.2 Constitutional (Structural) Isomerism 137
4.4.3 Stereoisomerism: In Place – Positional Isomers In Space – Optical Isomers
4.4.4 Isomer Preferences 144
4.5 Sophisticated Shapes 146
4.5.1 Compounds of Polydentate Ligands 146
4.5.2 Preorganised Complexes 147
4.5.3 Host–Guest Non?covalent Molecular Assemblies 152
4.5.4 Polymetallic Compounds 154
4.6 Defining Shape 158
Concept Keys 159
Further Reading 160
Chapter 5 Stability 161
5.1 Making a Stable Assembly 161
5.1.1 Thermodynamic Stability 161
5.1.2 Factors Influencing Stability of Metal Complexes 164
5.1.3 Overall Stability Constants 176
5.1.4 Undergoing Change – Kinetic Stability 179
5.2 Complexation – Will It Last? 182
5.2.1 Thermodynamic and Kinetic Relationships 182
5.2.2 Rate Coefficients 183
5.2.3 Lability and Inertness in Octahedral Complexes 184
5.3 Reaction Mechanisms 185
5.3.1 Substitution 186
5.3.2 Stereochemical Change 195
5.3.3 Reduction–Oxidation Reactions 201
5.3.4 Ligand?centred Reactions 211
Concept Keys 212
Further Reading 212
Chapter 6 Synthesis 214
6.1 Molecular Creation—Ways to Make Complexes 214
6.2 Core Metal Chemistry—Periodic Table Influences 214
6.2.1 s?Block: Alkali and Alkaline Earth Metals 214
6.2.2 p?Block: Metals and Non?metals 215
6.2.3 d?Block: Transition Metals 216
6.2.4 f?Block: Inner Transition Metals (Lanthanoids and Actinoids) 218
6.2.5 Beyond Natural Elements 220
6.3 Reactions Involving the Coordination Shell 221
6.3.1 Ligand Substitution Reactions in Aqueous Solution 221
6.3.2 Substitution Reactions in Non?aqueous Solvents 228
6.3.3 Substitution Reactions Without Using a Solvent 230
6.3.4 Chiral Complexes 232
6.3.5 Catalysed Reactions 234
6.4 Reactions Involving the Metal Oxidation State 234
6.5 Reactions Involving Coordinated Ligands 238
6.5.1 Metal?directed Reactions 238
6.5.2 Reactions of Coordinated Ligands 242
6.6 Organometallic Synthesis 247
6.7 Nanomolecular Synthesis 251
6.7.1 Traditional Coordination Complexes and Nanomolecules 251
6.7.2 Polyoxometalates and Other Clusters 253
6.8 Silicate and Aluminosilicate Synthesis 256
6.8.1 Silicates 256
6.8.2 Aluminosilicates 257
Concept Keys 259
Further Reading 260
Chapter 7 Properties 262
7.1 Investigative Methods 262
7.2 Physical Methods and Outcomes 263
7.3 Probing Complexes Using Physical Methods 268
7.3.1 Infrared (IR) Spectroscopy 270
7.3.2 Electronic Spectroscopy 274
7.3.3 Circular Dichroism (CD) 278
7.3.4 Magnetic Moment Measurement: The Gouy Method 282
7.3.5 Nuclear Magnetic Resonance (NMR) Spectroscopy 286
7.3.6 Electron Paramagnetic Resonance (EPR) Spectroscopy 289
7.3.7 Voltammetry 294
7.3.8 X?Ray Crystallography 299
7.3.9 A Tandem Technique: Electrospray Ionisation Mass Spectrometry 304
7.3.10 Computational Methods 307
Concept Keys 308
Further Reading 309
Chapter 8 A Complex Life 311
8.1 Metal Ions in the Natural World 311
8.1.1 Biological Ligands 313
8.1.2 Metals in Biology – Why Are They Needed? 323
Concept Keys 346
Further Reading 346
Chapter 9 Complexes and Commerce 347
9.1 Metals in Medicine 347
9.1.1 Introducing Metallodrugs 348
9.1.2 Anti?cancer Drugs 350
9.1.3 Other Metallodrugs 354
9.2 Medical Imaging and Diagnostics 356
9.2.1 Nuclear Imaging 356
9.2.2 Magnetic Resonance Imaging (MRI) 359
9.3 Analysing with Complexes 360
9.3.1 Fluoroimmunoassay 361
9.3.2 Fluoroionophores 362
9.4 Profiting from Complexation 363
9.4.1 Metal Extraction 363
9.4.2 Coordination Complexes as Industrial Catalysts 367
9.4.3 Complexes as Nanomaterials 372
9.5 Being Green 373
9.5.1 Complexation in Remediation 374
9.5.2 Better Ways to Fine Organic Chemicals 374
9.6 Complex Futures 375
Concept Keys 376
Further Reading 376
A Nomenclature 378
A.1 Nomenclature Basics 378
A.2 Ligand Polydenticity 381
A.3 Naming Coordination Compounds 382
A.3.1 Simple Ligands 382
A.3.2 Complexes 383
A.4 Organometallic Compounds 386
Further Reading 386
B Molecular Symmetry: The Point Group 387
Further Reading 392
Index 393
EULA 402

Produkt-Details

• Erscheint lt. Verlag: 23.12.2024
• Reihe/Serie: Inorganic Chemistry: A Textbook Series
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Anorganische Chemie
• Schlagworte: Analysis • bioinorganic chemistry • catalysis • Coordination • Coordination Compounds • Inorganic Chemistry • Ligands • mechanisms • metal complexes • metal extraction • metal ions • metal-ligand bonding • Metallodrugs • Metalloenzymes • Metalloproteins • molecular structure • Molecular symmetry • Nomenclature • organometallic compounds • polymetallic compounds • Properties • Reactions • spectroscopy • stereochemistry • synthesis • Thermodynamic Stability
• ISBN-10: 1-394-19072-7 / 1394190727
• ISBN-13: 978-1-394-19072-0 / 9781394190720