Full Description
Suitable for graduate students, master courses and postdocs, this is the first textbook to discuss the whole range of contemporary coordination chemistry. It has been thoroughly reviewed by leading textbook authors, and the concept already proven by the successful Spanish edition.
After an introduction, the book covers in a clearly ordered manner structure and bonding, supramolecular coordination chemistry, electronic properties and electron transfer.
Set to become the standard for years to come.
Contents
Preface XXIII
Introduction XXIX
Part One Structure and Bonding
1 Bonding in Coordination Compounds 3
1.1 d Wavefunctions 3
1.2 Crystal Field Effect on Wavefunctions 3
1.3 Molecular Orbital Theory 11
1.4 Angular Overlap Model 24
2 Classifi cation of Ligands and Design of Coordination 31
2.1 Introduction 31
2.2 Classifi cation of Ligands According to Their Dentate Nature 32
2.3 Versatile Ligands 47
3 Stereochemistry and Distortions in Coordination Compounds 59
3.1 Stereochemistry 59
3.2 Distortions in Coordination Compounds Due to Electronic Factors: Jahn-Teller Effect 81
4 Isomerism in Coordination Compounds 95
4.1 Introduction 95
4.2 Constitutional or Structural Isomers 95
4.3 Stereoisomers 99
4.4 Chirality in Coordination Compounds: Nomenclature of Chirality 103
4.5 Chirality in Coordination Compounds: Origin and Examples in Mononuclear Complexes 107
4.6 Chirality in Polynuclear Coordination Compounds: Examples 111
4.7 Separation of Chiral Isomers 113
4.8 From Chirality (Coordination Compounds) to Chirality (Application to the Enantioselective Synthesis of Organic Molecules) 118
4.9 Valence Tautomerism 122
5 Polynucleating Ligands: From Di- and Polynuclear Complexes to Nanomolecules 129
5.1 Introduction 129
5.2 Polynucleating Ligands 129
5.3 Building Block Strategy or Controlled Synthesis: Complexes as Metals/Complexes as Ligands (Complexes as Tectons) 133
5.4 High Nuclearity Clusters: Generalities 135
5.5 Oxido-hydroxido High-nuclearity Clusters (Excluding Polyoxometalates) 135
5.6 Polyoxometalates (POMs) 138
5.7 Oxido-carboxylate Clusters (Especially Those Derived from [M3O(carboxylate)6] Units) 145
5.8 Metal Wheels 148
5.9 Other Signifi cant Organic Polynucleating Ligands 149
5.10 Metallodendrimers 152
5.11 Future Outlook 157
6 Metal-Metal Bond and Metal Clusters 163
6.1 Introduction: Defi nition and Main Characteristics 163
6.2 Transition Metal Clusters 163
6.3 Transition Metal Clusters with π-Donor Ligands 164
6.4 Clusters with π-Acid Ligands: Structure and Bonding 170
6.5 Main Group Metal Clusters 183
6.6 Clusters with Interstitial Atoms 188
6.7 Gold Clusters and Nanoparticles 190
7 Thermodynamic and Non-redox Kinetic Factors in Coordination Compounds 199
7.1 Thermodynamic Stability 200
7.2 Non-redox Reaction Mechanisms 217
Part Two Electronic Properties
8 Crystal Field Theory and Spin-Orbit Coupling: Energy Terms and Multiplets 237
8.1 Introduction: The Atomic/Electronic Hamiltonian 237
8.2 Application of Atomic and Spin Hamiltonians to Many-electron Wavefunctions: Terms, Multiplets and Magnetic States 238
8.3 Weak Field Method 242
8.4 Strong Field Method 252
8.5 Correlations Between the Energy Terms Derived from the Weak and Strong Fields: Intermediate Fields 254
8.6 Tanabe-Sugano Diagrams 257
8.7 Ligand Field 259
8.8 Spin-Orbit Coupling 261
8.9 Final Considerations on Spin-Orbit Coupling and Zero Field Splitting 270
9 Electronic Spectroscopy 273
9.1 Introduction 273
9.2 Electromagnetic Radiation 273
9.3 Fundamentals of Spectroscopy: Selection Rules 275
9.4 Interpretation of the Selection Rules 278
9.5 Types of Spectra for Transition Metal Complexes 281
9.6 Calculating the Crystal Field Parameters from the Position of the d-d Bands 292
10 Molecular Magnetism 295
10.1 Mononuclear Complexes 295
10.2 Polynuclear Complexes 311
10.3 Spin Transitions (Spin Crossover (SCO)) 333
11 Electron Paramagnetic Resonance in Coordination Compounds 341
11.1 Introduction 341
11.2 Fundamentals of EPR Spectroscopy 341
11.3 Systems Suitable for Research with EPR 342
11.4 Recording EPR Spectra and Their Information 343
11.5 g Values 344
11.6 Hyperfi ne Coupling 345
11.7 Isotropic Polyelectronic Systems 352
11.8 Study of the Anisotropy in Monoelectronic Systems with Orbitally Non-degenerate Ground States 353
11.9 Zero-fi eld Splitting: Anisotropic Polyelectronic Systems (S > 1/2) 357
11.10 EPR Spectra of Polynuclear Metal Complexes 366
11.11 EPR Spectra of Orbitally Degenerate Terms 368
11.12 High-frequency and High-fi eld EPR Spectroscopy 368
11.13 Relaxation Times and Linewidths in EPR 369
Part Three Electron Transfer
12 Redox Mechanisms 377
12.1 Historical Introduction 377
12.2 Mechanisms of Redox Reactions 377
13 Mixed-valence Compounds 403
13.1 Introduction 403
13.2 Experimental Features 403
13.3 Defi nition, Stability and Electronic Delocalization 404
13.4 Electrons Jumping from One Center to Another 406
13.5 The Robin-Day Classifi cation 407
13.6 Theory of Mixed-valence Compounds 407
13.7 Degree of Delocalization: Factors Favoring Localization or Delocalization 415
13.8 Conclusions 431
Part Four New Trends in Modern Coordination Chemistry
14 Supramolecular Chemistry, Metallosupramolecular Chemistry and Molecular Architecture 439
14.1 Supramolecular Chemistry: Defi nitions 439
14.2 Molecular Recognition 442
14.3 Supramolecular Dynamics: Reactivity, Catalysis and Transport Processes 451
14.4 The Self-assembly Concept and Its Application in Molecular and Supramolecular Chemistry 451
14.5 Metallosupramolecular Chemistry: Different Strategies and Types 452
14.6 Encapsulated Guests in Metallo-nanostructures 463
14.7 Supramolecular Assistance in the Synthesis of Molecular (and Supramolecular) Structures 463
14.8 (Supra)molecular Devices and Machines 468
15 Photochemistry and Photophysics in Coordination Compounds 477
15.1 Fundamentals 477
15.2 Examples of Main Photochemical Processes 485
15.3 Photo-molecular Devices and Machines 493
15.4 Applications (Present and Future) 505
16 Crystal Engineering: Metal-Organic Framework (MOFs) 521
16.1 Coordination Polymers and Crystal Engineering 521
16.2 MOFs with Polydentate Polypyridyl Derivatives 526
16.3 MOFs with Carboxylate Linkers 531
16.4 MOFs with Polynuclear Building Nodes 533
16.5 Highly Connected Solid-state Materials 537
16.6 Interpenetrating MOFs 539
16.7 Porous Coordination Polymers 541
16.8 Inorganic Hybrid Materials 546
17 Biocoordination Chemistry: Coordination Chemistry and Life 555
17.1 Introduction 555
17.2 Biological Ligands and Their Environment 558
17.3 Systems that Interact with O2 563
17.4 Electron Transfer 570
17.5 Electron Transport and Enzyme Activity 573
17.6 Medicinal Coordination Chemistry 578
References 581
Appendix 1: Tanabe-Sugano Diagrams (Chapter 8) 583
Appendix 2: Definitions and Units in Molecular Magnetism (Chapter 10) 587
Appendix 3: cm formulae for some homodinuclear, dn-dn, and heterodinuclear, dn-dn, complexes (Chapter 10) 589
Index 591
