Introduction to Coordination Chemistry

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
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
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
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
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
6 Synthesis
7 Properties
8 A Complex Life
9 Complexes and Commerce
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