Coordination Chemistry: Basics and Current Trends

Description

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. 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