Coordination Chemistry (eBook)

Front Cover 1
Coordination Chemistry 4
Copyright Page 5
Table of Contents 6
Organizing Committee 8
PREFACE 10
CHAPTER 1. A REVIEW OF SOME VERY NEW DEVELOPMENTS IN THE STEREOCHEMISTRY OF COORDINATION COMPOUNDS 12
References 18
CHAPTER 2. COMPLEX CHEMISTRY AND THE MIMICRY OF METALLO-ENZYMES 20
INTRODUCTION 20
THE NITROGENASE REACTION 21
ALKYLATION OF LIGATING DINITROGEN 21
PECULIAR AFFINITY OF [M(N2)(dppe)2] FOR LIGANDS 22
AMMONIA AS A BACK-BONDING LIGAND 23
REFERENCES 24
CHAPTER 3. SYNTHETIC OXYGEN CARRIERS RELATED TO NATURAL SYSTEMS 26
INTRODUCTION 26
C0BALT(II)-SCHIFF-BASE COMPLEXES 26
IRON(II) PORPHYRIN COMPLEXES 27
MANGANESE(II) PORPHYRINS 29
CAPPED PORPHYRIN IRON(ll) COMPLEXES 30
REFERENCES 36
CHAPTER 4. STABILITY, STRUCTURE AND REACTIVITY OF MIXED LIGAND COMPLEXES IN SOLUTION 38
1. INTRODUCTION 38
2. CHARACTERIZATION OF THE STABILITY OF TERNARY COMPLEXES 39
3. INDIRECT INTERACTIONS IN TERNARY COMPLEXES 40
4. INTRAMOLECULAR LIGAND-LIGAND INTERACTIONS IN TERNARY COMPLEXES 44
5. CONCLUSIONS 52
REFERENCES 53
CHAPTER 5. SOME RECENT ADVANCES IN THE UNDERSTANDING OF THE MECHANISM OF THE BASE HYDROLYSIS OF OCTAHEDRAL COBALT(III) COMPLEXES 58
INTRODUCTION AND MECHANISM 58
DETECTION OF SYSTEMS WHERE PROTON TRANSFER IS NOT FAST COMPARED TO BASE HYDROLYSIS 60
INFORMATION TO BE GAINED FROM SYSTEMS WHERE 62
THE REACTIVITY PATTERN OF CHLORO-PENTA-AMINE COBALT(III) COMPLEXES. 63
CONCLUSIONS 65
REFERENCES 65
CHAPTER 6. PHOTOCHEMICAL PATHS: THE PHOTOCHEMICAL AND PHOTOPHYSICAL LIMITS 68
Abstract 68
Introduction 68
Thexi State Reactivity 68
References 73
CHAPTER 7. ORBITAL SYMMETRY AND SUBSTITUTION-RATE EFFECTS ON REDOX REACTIONS: Ru(III)-Ti(III) ELECTRON TRANSFERS 76
INTRODUCTION 76
OUTER-SPHERE REACTIONS 77
INNER-SPHERE REACTIONS 78
SUBSTITUTION RATES 78
RATE CONTROL BY ELECTRON TRANSFER 78
ADJACENT AND REMOTE ATTACK 78
THE NATURE OF THE Ti(IV) PRODUCTS 80
LIGAND EFFECTS ON Ti(III) SUBSTITUTIONS 80
CONCLUSION 80
ACKNOWLEDGEMENT 80
REFERENCES 81
CHAPTER 8. METAL COMPLEXES WITH FUNCTIONALIZED MAGROCYCLIC LIGANDS 82
INTRODUCTION 82
SYNTHESIS 83
METAL COMPLEXES AND THEIR PROPERTIES 86
REFERENCES 90
CHAPTER 9. FOURTEEN: A MAGIC NUMBER OF COORDINATION CHEMISTRY 92
SOME REMARKS ON THE STABILITY OF CYANO COMPLEXES 93
ELIMINATION OF INTERFERENCES IN ATOMIC A3S0RPTI0N SPECTROMETRY OF TRANSITION METAL IONS BY CYANIDE 96
PHOTOAQUATION OF HEXACYANOFERRATE(II) AND OCTACYANOMOLYBDATE( IV) 99
PREBIOTIC IMPORTANCE OF THE 2/14 ISOELECTRONIC SPECIES 103
REACTIONS OF NITROSYLPENTACYANOFERRATE(II) WITH ORGANIC COMPOUNDS CONTAINING ONE OR MORE PRIMARY AMINO GROUPS 106
REFERENCES 108
CHAPTER 10. THE INSERTION REACTION OF UNSATURATED HYDROCARBONS INTO METAL —HYDROGEN BONDS 110
INTRODUCTION 110
THE ALKENE AND ALKYNE INSERTION REACTIONS INTO PLATINUM-HYDROGEN BONDS 111
REFERENCES 116
CHAPTER 11. COORDINATION COMPOUNDS WITH INORGANIC HIGH-MOLECULAR LIGANDS 118
References 127
CHAPTER 12. METAL ION CATALYSED REACTIONS OF COORDINATED OXALATE 130
MEASUREMENTS OF REACTION RATES AT HIGH PRESSURES 134
EXPERIMENTAL 138
ACKNOWLEDGEMENTS 138
REFERENCES 138
CHAPTER 13. TRENDS TOWARDS THE STUDY OF LOW MOLECULAR WEIGHT COMPLEXES IN BIOLOGICAL SYSTEMS 140
INTRODUCTION 140
CONCLUSIONS 149
REFERENCES 149
CHAPTER 14. METAL CHELATES AS ANTI-CANCER AGENTS 152
REFERENCES 159
CHAPTER 15. NITROGEN FIXATION: PAST PROGRESS AND RECENT ADVANCES 160
INTRODUCTION 160
NITROGEN REDUCTION IN PROTIC MEDIA 160
NITROGEN PHOTOREDUCTION 167
REFERENCES 168
CHAPTER 16. BINUCLEAR COMPLEXES IN ELECTRON TRANSFER REACTIONS 170
1. THE THERMAL PROCESS: MECHANISM. 171
2. THE THERMAL PROCESS: RATE OF ELECTRON TRANSFER. 173
3. THE OPTICAL PROCESS. 176
REFERENCES 182
CHAPTER 17. REGIO- AND STEREOSELECTIVITY IN SUBSTITUTION AND REDOX REACTIONS OF OXO-TRANSITION METAL COMPLEXES 184
INTRODUCTION 184
REGIOSELECTIVE SUBSTITUTION OF OXOVANADIUM(IV) COMPLEXES 186
ELECTRON TRANSFER THROUGH THE BASAL SITE 187
OUTER SPHERE OXIDATION OF OXOVANADIUM(IV) AND -MOLYBDENUM(V) COMPLEXES 188
STEREOSELECTIVITY ON OUTER SPHERE REDOX REACTIONS INVOLVING OPTICAL ISOMERS 189
REFERENCES 192
CHAPTER 18. THE MUTUAL INFLUENCE OF LIGANDS IN COORDINATION COMPOUNDS 194
INTROOUCTION 194
THE INFLUMOS OF SUBSTITUTION OU BOUD STRENGTH 194
TRANS AND INFULENCE III COORDINATION COMPOUNDS 196
INFLUENCE PARAMETERS - QUANTITATIVE CHARACTERISTICS OF THE CAPACITY OF LIGANDS TO EXERT MUTUAL INFLUENCE 197
REFERENCES 201
CHAPTER 19. RECENT TRENDS IN THE APPLICATION OF COORDINATION CHEMISTRY IN BIOLOGY AND MEDICINE 202
INTRODUCTION 202
TRANSPORT OF COPPER BY AMINO ACIDS 202
TRANSPORT OF COPPER BY ALBUMIN 205
STRUCTURE OF THE COPPER TRANSPORT SITE OF HUMAN ALBUMIN 206
APPLICATIONS IN COPPER-RELATED DISEASES 208
MENKE'S DISEASE 210
REFERENCES 211
CHAPTER 20. MODERN ASPECTS OF STRUCTURE/REACTIVITY PROBLEMS FOR COORDINATION COMPOUNDS 212
INTRODUCTION. VIBRONIC INTERACTION EFFECTS 212
THE MAIN AREAS OF MANIFESTATIONS OF VIBRONIC EFFECTS 215
THE CONCEPTUAL FRAMEWORK OF VIBRONIC COUPLING 215
ORBITAL VIBRONIC CONSTANTS AS PARAMETERS OF MOLECULAR STRUCTURE 217
THE CHANGE OF CHEMICAL REACTIVITY 219
PARAMETRIZATION 223
EXAMPLES: ACTIVATION OF CARBON MONOXIDE, NITROGEN AND NITROGEN MONOXIDE MOLECULES BY COORDINATION 224
REFERENCES 228
CHAPTER 21. THE APPLICATION OF CONFORMATIONAL ANALYSIS TO THE STRUCTURE AND ENERGY OF COORDINATION COMPOUNDS WITH SPECIAL REFERENCE TO CHELATE RINGS 230
INTRODUCTION 230
REFERENCES 238
CHAPTER 22. COORDINATION CHEMISTRY: A QUEST FOR IDENTITY 240
ABSTRACT 240
CHAPTER 23. LIGAND POLARIZATION TRANSITION PROBABILITIES IN LANTHANIDE AND TRANSITION-METAL COMPLEXES 246
INTRODUCTION 246
LIGAND POLARIZATION TRANSITION PROBABILITIES 247
THE INTENSITIES OF d-d AND f-f TRANSITIONS 249
THE OPTICAL ACTIVITY OF CHIRAL METAL COMPLEXES 253
REFERENCES 257
CHAPTER 24. THE CHEMISTRY OF THE TRANSITION METAL DIALKYLAMIDES 260
REFERENCES 264
CHAPTER 25. RECENT STUDIES IN THE SYNTHETIC AND STRUCTURAL CHEMISTRY OF THE TRANSITION METALS 266
INTRODUCTION 266
UNUSUAL OXIDATIVE REACTIONS OF TRANSITION METAL DITHIOCARBAMATES 266
SYNTHESIS AND STRUCTURE OF CAPPED SCHIFF BASE COMPLEXES 269
SYNTHESIS AND STRUCTURE OF 1,9-DISUBSTITUTED PHENALENE COMPLEXES 273
REFERENCES 276
CHAPTER 26. LINEAR FREE ENERGY RELATIONSHIPS IN COORDINATION CHEMISTRY 278
I. Introduction 278
II. RELATIONSHIPS BETWEEN THE STABILITY CONSTANTS OP C0:!PI£XES AND HIE ACIDITY AHD BASICITY OF THE LIGANDS 279
REFERENCES 286