The Chemistry of Complex Compounds is ideally prepared in this textbook for undergraduate chemistry students, providing both an easy and comprehensive introduction to the subject, which is relevant to examinations. It is based on proven lecture notes and assumes no basic knowledge. In addition to basic questions such as "what are complexes" and "what are organometallic compounds", the common bonding models are presented and the colour and stability of coordination compounds are explained, among other things. Other chapters cover redox reactions in complexes, the metal-metal bond, molecular magnetism, supramolecular chemistry, and bioinorganic chemistry. As a conclusion, the book gives an outlook into current research areas and trends in coordination chemistry, so that students of higher semesters and PhD students will also benefit from reading it. This includes the luminescence of complexes and selected examples of reactions catalyzed by complexes. Birgit Weber is a professor of inorganic chemistry at the University of Bayreuth. Her research focuses on coordination chemistry and ligand design for multifunctional switchable complexes.
Author(s): Birgit Weber
Publisher: Springer Spektrum
Year: 2023
Language: English
Pages: 272
City: Berlin
Notes on the First Edition
Notes on the Second Edition
Acknowledgements
Contents
1: What Are Complexes?
1.1 History
1.1.1 Synthesis of Cobalt Ammine Complexes
1.1.2 Complexes According to Werner: An Ingenious Impertinence
1.2 Bonding
1.3 Questions
2: Structure and Nomenclature
2.1 IUPAC Nomenclature of Coordination Compounds
2.1.1 Establishment of the Formulae of Coordination Compounds
2.1.2 Names of Coordination Compounds
2.2 Nomenclature of Organometallic Compounds
2.2.1 Ligand Names for Organometallic Compounds
2.3 Information on the Structure
2.3.1 The μ Convention
2.3.2 The η Convention
2.3.3 The κ Convention
2.4 Structure of Complexes
2.4.1 Ligands and Their Denticity
2.4.2 Coordination Numbers and Coordination Polyhedra
2.5 Isomerism in Coordination Compounds
2.5.1 Stereoisomerism
2.5.2 Enantiomers
2.6 Questions
3: What Are Organometallic Compounds?
3.1 History
3.2 The 18-Electron Rule
3.2.1 Counting Electrons
3.3 Important Reactions in Organometallic Chemistry
3.3.1 Coordination and Release of Ligands
3.3.2 Oxidative Addition and Reductive Elimination
3.3.3 Insertion of Olefins and β-H Elimination
3.3.4 Oxidative Coupling and Reductive Cleavage
3.3.5 α-H Elimination and Carbene Insertion
3.4 Questions
4: Bond Theories
4.1 Electron Configuration and Term Symbols
4.1.1 Quantum Numbers
4.1.2 Term Symbols
Determination of Term Symbols
4.2 The Valence-Bond (VB) Theory
4.3 The Ligand Field Theory
4.3.1 Octahedral Ligand Field
4.3.2 Crystal Field Stabilization Energy and the Spectrochemical Series
4.3.3 High-Spin and Low-Spin
4.3.4 Non-Octahedral Ligand Fields
4.4 The Molecular Orbital (MO) Theory
4.4.1 σ and π Interactions Between Ligand and Central Atom
4.4.2 MO Scheme of a σ Complex
4.4.3 MO Scheme of a π Complex
4.5 Questions
5: Color of Coordination Compounds
5.1 Why Are Complexes Coloured?
5.2 Selection Rules for Electronic Transitions
5.3 Charge Transfer (CT) Transitions
5.4 d-d Transitions and the Determination of ΔO
5.4.1 Tanabe-Sugano Diagrams
5.4.2 trans-[CoCl2(en)2]Cl and cis-[CoCl2(en)2]Cl
5.5 Questions
6: Stability of Coordination Compounds
6.1 What Is a Stable Complex?
6.1.1 The HSAB Concept
6.2 Thermodynamic Stability and Inertness of Complexes
6.3 The Chelate Effect
6.3.1 Chelation Therapy
6.3.2 Radiotherapy and MRI
6.4 The Trans Effect
6.4.1 Interpretation of the Trans Effect
6.4.2 Cisplatin and the Trans Effect
6.5 Questions
7: Redox Reactions of Coordination Compounds
7.1 Blue Copper Proteins
7.1.1 The Jahn-Teller Effect
Jahn-Teller Theorem
7.2 Redox Reactions in Coordination Compounds
7.2.1 The Outer Sphere Mechanism
7.2.2 Inner Sphere Mechanism
7.3 Non-Innocent Ligands Using the Example of NO
7.3.1 Complexes with Redox-Active Ligands
7.4 Questions
8: Supramolecular Coordination Chemistry
Definition of Supramolecular Chemistry According to Lehn
8.1 Molecular Recognition
8.1.1 The Template Effect
Definition of Template Synthesis According to Busch
Definition of Molecular Recognition
8.2 Helicates
Definition of Self-Organisation
8.3 MOFs - Metal-Organic Frameworks
8.3.1 Coordination Polymer or MOF?
8.3.2 The Structure of MOFs
8.3.3 Advantages and Potential Applications
8.4 Questions
9: Metal-Metal Bond
9.1 Nomenclature for Polynuclear Complexes/Metal-Metal Bonds
9.2 Metal-Metal Single Bond
9.2.1 The EAN Rule
9.2.2 MO Theory
9.3 Multiple Metal-Metal Bonds
9.3.1 Higher, Stronger, Shorter: Metal-Metal Quintuple Bond
9.4 Cluster Complexes
9.4.1 The Isolobal Analogy
The Isolobal Analogy
9.4.2 The Wade Rules for Boran Clusters
9.4.3 The Wade-Mingos Rules
9.5 Questions
10: Magnetism
10.1 Units
10.2 Magnetic Properties of Matter
10.2.1 Diamagnetism
10.2.2 Paramagnetism
10.3 The Magnetic Moment
10.3.1 Origin of the Magnetic Moment
10.3.2 Spin-Orbit and j-j Coupling
10.4 Temperature Dependence of the Magnetic Moment
10.5 Cooperative Magnetism
10.5.1 Exchange Interactions
10.5.2 Magnetism of Metals
10.5.3 Orthogonal Orbitals
10.5.4 Microstructure of Ferromagnets
10.6 Spin Crossover
10.6.1 Theoretical Considerations
10.6.2 Pressure Dependence
10.6.3 Switching with Light: The LIESST Effect
10.6.4 Cooperative Interactions and Hysteresis
10.7 Questions
11: Luminescence of Metal Complexes
11.1 Basics
11.2 Fluorescence Using the Example of a Zinc(II) Complex
11.2.1 Prerequisites for Fluorescence
11.3 Phosphorescence of Diamagnetic Complexes
11.3.1 d6 [M(bipy)3]2+ Complexes
11.3.2 Copper(I) Complexes as Example of 3d10
11.4 Phosphorescence of Metal-Centered Transitions
11.5 Luminescence by Aggregation of Platinum(II) Complexes
11.6 Questions
12: Bioinorganic Chemistry
12.1 Biologically Relevant Iron Complexes
12.1.1 Model Compounds
12.2 Oxygen Transport Using the Example of Hemoglobin
What Does 1Δ and 1Σ Actually Mean for Singlet Oxygen?
12.2.1 Oxygen Complexes
12.2.2 Bonding Situation in Hemoglobin
12.2.3 Model Compounds for Hemoglobin and Myoglobin
12.3 Cobalamins: Stable Organometallic Compounds
12.3.1 Bioavailability of Elements
12.3.2 Structure
12.3.3 Reactivity
12.4 Questions
13: Catalysis
13.1 Catalyst
13.2 Preparation of Polyethylene (PE)
13.2.1 Ziegler´s Build-Up and Displacement Reaction
13.2.2 The Nickel Effect
13.2.3 Polymerisation of Ethylene by the Low Pressure Process
13.2.4 Chain Termination Reactions
13.3 Polypropylene
13.3.1 Regioselectivity
13.3.2 Stereoselectivity
13.4 Photocatalysis
13.4.1 Basics
13.4.2 Photosynthesis
13.4.3 Photocatalytic Water Splitting
13.5 Questions
References
