Free download Introduction to Coordination Chemistry By Geoffrey A. Lawrance

Authors of:  Introduction to Coordination Chemistry By Geoffrey A. Lawrance

Geoffrey A. Lawrance

Table of Contents in Introduction to Coordination Chemistry By Geoffrey A. Lawrance

Preface  

Preamble  

1 The Central Atom  

1.1 Key Concepts in Coordination Chemistry  

1.2 A Who’s Who of Metal Ions  

1.2.1 Commoners and ‘Uncommoners’  

1.2.2 Redefining Commoners  

1.3 Metals in Molecules  

1.3.1 Metals in the Natural World  

1.3.2 Metals in Contrived Environments  

1.3.3 Natural or Made-to-Measure Complexes  

1.4 The Road Ahead  

Concept Keys  

Further Reading  

2 Ligands  

2.1 Membership: Being a Ligand  

2.1.1 What Makes a Ligand?  

2.1.2 Making Attachments – Coordination  

2.1.3 Putting the Bite on Metals – Chelation  

2.1.4 Do I Look Big on That? – Chelate Ring Size  

2.1.5 Different Tribes – Donor Group Variation  

2.1.6 Ligands with More Bite – Denticity  

2.2 Monodentate Ligands – The Simple Type  

2.2.1 Basic Binders  

2.2.2 Amines Ain’t Ammines – Ligand Families  

2.2.3 Meeting More Metals – Bridging Ligands  

2.3 Greed is Good – Polydentate Ligands  

2.3.1 The Simple Chelate  

2.3.2 More Teeth, Stronger Bite – Polydentates  

2.3.3 Many-Armed Monsters – Introducing Ligand Shape  

2.4 Polynucleating Species – Molecular Bigamists  

2.4.1 When One is Not Enough  

2.4.2 Vive la Difference – Mixed-metal Complexation  

2.4.3 Supersized – Binding to Macromolecules  

2.5 A Separate Race – Organometallic Species  

Concept Keys  

Further Reading

3 Complexes  

3.1 The Central Metal Ion  

3.2 Metal–Ligand Marriage  

3.2.1 The Coordinate Bond  

3.2.2 The Foundation of Coordination Chemistry  

3.2.3 Complex Shape – Not Just Any Which Way  

3.3 Holding On – The Nature of Bonding in Metal Complexes  

3.3.1 An Ionic Bonding Model – Introducing Crystal Field Theory  

3.3.2 A Covalent Bonding Model – Embracing Molecular Orbital Theory  

3.3.3 Ligand Field Theory – Making Compromises  

3.3.4 Bonding Models Extended  

3.4 Coupling – Polymetallic Complexes  

3.5 Making Choices  

3.5.1 Selectivity – Of all the Molecules in all the World, Why This One?  

3.5.2 Preferences – Do You Like What I Like?  

3.5.3 Complex Lifetimes – Together, Forever?  

3.6 Complexation Consequences  

Concept Keys  

Further Reading  

4 Shape  

4.1 Getting in Shape  

4.2 Forms of Complex Life – Coordination Number and Shape  

4.2.1 One Coordination (ML)  

4.2.2 Two Coordination (ML2)  

4.2.3 Three Coordination (ML3)  

4.2.4 Four Coordination (ML4)  

4.2.5 Five Coordination (ML5)  

4.2.6 Six Coordination (ML6)  

4.2.7 Higher Coordination Numbers (ML7 to ML9)  

4.3 Influencing Shape  

4.3.1 Metallic Genetics – Metal Ion Influences  

4.3.2 Moulding a Relationship – Ligand Influences  

4.3.3 Chameleon Complexes  

4.4 Isomerism – Real 3D Effects  

4.4.1 Introducing Stereoisomers  

4.4.2 Constitutional (Structural) Isomerism  

4.4.3 Stereoisomerism: in Place – Positional Isomers; in Space – Optical Isomers  

4.4.4 What’s Best? – Isomer Preferences  

4.5 Sophisticated Shapes  

4.5.1 Compounds of Polydentate Ligands  

4.5.2 Encapsulation Compounds  

4.5.3 Host–Guest Molecular Assemblies  

4.6 Defining Shape  

Concept Keys  

Further Reading  

5 Stability  

5.1 The Makings of a Stable Relationship  

5.1.1 Bedded Down – Thermodynamic Stability  

5.1.2 Factors Influencing Stability of Metal Complexes  

5.1.3 Overall Stability Constants  

5.1.4 Undergoing Change – Kinetic Stability  

5.2 Complexation – Will It Last?  

5.2.1 Thermodynamic and Kinetic Stability  

5.2.2 Kinetic Rate Constants  

5.2.3 Lability and Inertness in Octahedral Complexes  

5.3 Reactions  

5.3.1 A New Partner – Substitution  

5.3.2 A New Body – Stereochemical Change  

5.3.3 A New Face – Oxidation–Reduction  

5.3.4 A New Suit – Ligand-centred Reactions  

Concept Keys  

Further Reading  

6 Synthesis  

6.1 Molecular Creation – Ways to Make Complexes  

6.2 Core Metal Chemistry – Periodic Table Influences  

6.2.1 s Block: Alkali and Alkaline Earth Metals  

6.2.2 p Block: Main Group Metals  

6.2.3 d Block: Transition Metals  

6.2.4 f Block: Inner Transition Metals (Lanthanoids and Actinoids)  

6.2.5 Beyond Natural Elements  

6.3 Reactions Involving the Coordination Shell  

6.3.1 Ligand Substitution Reactions in Aqueous Solution  

6.3.2 Substitution Reactions in Nonaqueous Solvents  

6.3.3 Substitution Reactions without using a Solvent  

6.3.4 Chiral Complexes  

6.3.5 Catalysed Reactions  

6.4 Reactions Involving the Metal Oxidation State  

6.5 Reactions Involving Coordinated Ligands  

6.5.1 Metal-directed Reactions  

6.5.2 Reactions of Coordinated Ligands  

6.6 Organometallic Synthesis  

Concept Keys  

Further Reading  

7 Properties  

7.1 Finding Ways to Make Complexes Talk – Investigative Methods  

7.2 Getting Physical – Methods and Outcomes  

7.3 Probing the Life of Complexes – Using Physical Methods  

7.3.1 Peak Performance – Illustrating Selected Physical Methods  

7.3.2 Pretty in Red? – Colour and the Spectrochemical Series

7.3.3 A Magnetic Personality? – Paramagnetism and Diamagnetism  

7.3.4 Ligand Field Stabilization  

Concept Keys  

Further Reading  

8 A Complex Life  

8.1 Life’s a Metal Ion  

8.1.1 Biological Ligands  

8.1.2 Metal Ions in Biology  

8.1.3 Classes of Metallobiomolecules  

8.2 Metalloproteins and Metalloenzymes  

8.2.1 Iron-containing Biomolecules  

8.2.2 Copper-containing Biomolecules  

8.2.3 Zinc-containing Biomolecules  

8.2.4 Other Metal-containing Biomolecules  

8.2.5 Mixed-Metal Proteins  

8.3 Doing What Comes Unnaturally – Synthetic Biomolecules  

8.4 A Laboratory-free Approach – In Silico Prediction  

Concept Keys  

Further Reading  

9 Complexes and Commerce  

9.1 Kill or Cure? – Complexes as Drugs  

9.1.1 Introducing Metallodrugs  

9.1.2 Anticancer Drugs  

9.1.3 Other Metallodrugs  

9.2 How Much? – Analysing with Complexes  

9.2.1 Fluoroimmunoassay  

9.2.2 Fluoroionophores  

9.3 Profiting from Complexation  

9.3.1 Metal Extraction  

9.3.2 Industrial Roles for Ligands and Coordination Complexes  

9.4 Being Green  

9.4.1 Complexation in Remediation  

9.4.2 Better Ways to Synthesize Fine Organic Chemicals  

9.5 Complex Futures  

9.5.1 Taking Stock  

9.5.2 Crystal Ball Gazing  

Concept Keys  

Further Reading  

Appendix A: Nomenclature  

Appendix B: Molecular Symmetry: The Point Group  

Index

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