Molybdenum (eBook)

Front Cover 1
Molybdenum: An Outline of its Chemistry and Uses 4
Copyright Page 5
Table of Contents 10
PREFACE 6
LIST OF CONTRIBUTORS 8
Chapter 1. OCCURRENCE, EXTRACTION, PRODUCTION AND USES OF MOLYBDENUM 20
1. INTRODUCTION 20
2. GEOLOGICAL ORIGIN 20
3. GEOCHEMISTRY OF PORPHYRIES 22
4. DISTRIBUTION 26
5. MINING 26
6. BENEFICATION 28
7. TECHNICAL GRADE MoO3 31
8. PURE MoO3 AND MOLYBDATES 33
9. WET CHEMICAL PROCESS 34
10. MOLYBDENUM DISULPHIDE 38
11. MOLYBDENUM METAL 39
12. PRODUCTION OF Mo METAL 41
13. CHEMICAL AND PHYSICAL PROPERTIES OF Mo 44
14. MOLYBDEUM HEXACARBONYL [Mo(CO)6] 45
15. THE INDUSTRIAL USES OF Mo AND ITS BASIC COMPOUNDS 48
16. LUBRICATION (SOLID) 49
17. OIL SOLUBLE Mo COMPOUNDS (E.P. LUBRICANTS) 53
18. INCORPORATION IN PLASTICS 56
19. BATTERIES 57
20. CORROSION INHIBITION 59
21. BASIC DYE COMPLEX PIGMENTS 68
22. PIGMENTS AND INKS (ref. 185) 70
23. FIRE RETARDANCE AND SMOKE SUPPRESSION OF PLASTICS 70
24. APPLICATIONS OF Mo METAL 77
25. MOLYBDENUM METAL AND ITS ALLOYS 78
26. THE BINARY ALLOYS 80
27. Mo (SOLUTE) ALLOYING METAL IN STEELS 84
28. INTERSTITIAL COMPOUNDS 87
29. MOLYBDENUM CARBIDE 92
30. MOLYBDENUM NITRIDES 94
31. MOLYBDENUM BORIDES 96
32. MOLYBDENUM SILICIDES 99
33. AGRICULTURE AND HORTICULTURE 103
REFERENCES 106
Chapter 2. AN INTRODUCTION TO THE CHEMISTRY OF MOLYBDENUM 113
2.1 INTRODUCTION 113
2.2 PROPERTIES OF THE ELEMENT 113
2.3 CLASSIFICATION OF MOLYBDENUM COMPOUNDS 115
2.4 THE CONSTRUCTION OF E.N. VERSUS V.N. PLOTS (CALLED MLX PLOTS) 129
2.5 DISCUSSION OF INDIVIDUAL MLX CLASSES OF MOLYBDENUM COMPOUNDS 136
2.6 A DISCUSSION OF THE CHEMISTRY OF MOLYBDENUM IN VARIOUS LIGAND ENVIRONMENTS 146
2.7 COMPARISON OF GENERALTRENDS IN THE CHEMISTRIES OF CHROMIUM, MOLYBDENUM AND TUNGSTEN 154
2.8 CONCLUSION 156
APPENDIX TO CHAPTER 157
Chapter 3. THE OXIDE CHEMISTRY OF MOLYBDENUM 165
3.1 INTRODUCTION 165
3.2 BINARY OXIDES 166
3.3 MOLYBDENUM OXIDE HYDRATES 170
3.4 TERNARY OXIDES OF MOLYBDENUM 172
3.5 SUGGESTIONS FOR FURTHER READING 195
3.6 REFERENCES 196
CHAPTER 4. MOLYBDENUM SULPHUR CHEMISTRY 204
1. INTRODUCTION 204
2. THIOETHER CHEMISTRY 204
3. DITHIOLENE CHEMISTRY 206
4. 1,1-DITHIOLATE COMPLEXES 209
5. THIOLATO-COMPLEXES 219
6. MOLYBDENUM SULPHIDO- AND DISULPHIDO-COMPLEXES 229
7. MOLYBDENUM SULPHIDES 248
8. APPLICATIONS OF MOLYBDENUM SULPHUR COMPLEXES 249
9. POSTSCRIPT 249
REFERENCES 250
Chapter 5. THE HALIDES OF MOLYBDENUM 270
1. INTRODUCTION 270
2. MOLYBDENUM FLUORIDES 270
3. MOLYBDENUM CHLORIDES 274
4. MOLYBDENUM BROMIDES 284
5. MOLYBDENUM IODIDES 285
6. OXIDE HALIDES OF MOLYBDENUM 286
7. OXIDE-IODIDES OF MOLYBDENUM 290
8. SULPHIDE-HALIDES OF MOLYBDENUM 290
9. SELENIDE-CHLORIDES OF MOLYBDENUM 292
REFERENCES 292
Chapter 6. THE ORGANOMETALLIC AND METAL-ORGANIC CHEMISTRY OF MOLYBDENUM 296
1. INTRODUCTION 296
2 MOLYBDENUM CARBONYL 297
3 ISOCYANIDE COMPLEXES 311
4 CARBENE, ALKYLIDENE, VINYLIDENE, CARBYNE AND ALKYLIDYNE COMPLEXES 312
5 COMPOUNDS CONTAINING MOLYBDENUM-CARBON s BONDS 319
6 ALKENE, POLYENE AND SIMPLE ALKYNE COMPLEXES 323
7 ALLYL COMPLEXES 329
8 CYCLOPROPENYL, CYCLOBUTADIENE AND TRMETHYLENEMETHANE COMPLEXES 338
9 CYCLOPENTADIENYL COMPLEXES 339
10 ARENE AND RELATED COMPLEXES 370
11 NITROSYL COMPLEXES 376
12 DIALKYLAMIDO, ALKOXY AND RELATED COMPLEXES 387
13 THE METAL-METAL BOND, AND MOLYBDENUM CLUSTERS 395
14 References 402
Chapter 7. The Chemical Nature of the Molybdenum Centres in Enzymes 422
1. Introduction 422
2. The iron-molybdenum cofactor FeMoco 423
3. The molybdenum cofectoi Moco
4. Conclusions 434
5. Acknowledgements 434
References 435
Chapter 8. THE BIOCHEMISTRY OF MOLYBDENUM 438
1. INTRODUCTION 438
2. MOLYBDENUM IN EVOLUTION 439
3. GEOGRAPHICAL DISTRIBUTION OF MOLYBDENUM 441
4. THE MOLYBDENUM ENZYMES: GENERAL INFORMATION 441
5. PHYSICAL METHODS FOR ENZYME STUDY 444
6. GENERAL RELEVANT CHEMISTRY OF MOLYBDENUM 445
7. RATES OF REACTION 456
8. BIOLOGICAL PROBLEMS: GENERAL CONSIDERATIONS 457
9. MECHANISTIC CONSIDERATIONS IN PROTEINS: GENERAL CONSIDERATIONS 463
10. MOLYBDENUM ENZYMES 465
11. SUBSTITUTION FOR MOLYBDENUM 469
12. CONCLUSION 469
REFERENCES 469
Chapter 9. MOLYBDENUM REQUIREMENTS, TOXICITY AND NUTRITIONAL LIMITS FOR MAN AND ANIMALS 471
1. INTRODUCTION 471
REFERENCES 491
Chapter 10. MOLYBDENUM COMPOUNDS IN HETEROGENEOUS CATALYSIS 496
1. INTRODUCTION 496
2. CATALYTIC PROPERTIES OF MoO3 AND MOLYBDATES 500
3. CATALYTIC PROPERTIES OF HETEROPOLYMOLYBDATES 558
4. SUPPORTED MoO3 CATALYSTS 578
5. MOLYBDENUM SULPHIDES AS CATALYSTS 596
6. REFERENCES 627
Chapter 11. HOMOGENEOUS COORDINATION CATALYSIS WITH MOLYBDENUM COMPLEXES 637
1 INTRODUCTION 637
2. MOLYBDENUM CATALYZED EPOXIDATIONS 637
3. OXOMOLYBDENUM COMPLEXES AS CATALYSTS FOR OXYGEN TRANSFER 640
4. HETEROPOLYCOMPOUNDS AS CATALYSTS 642
5. MOLYBDENUM CATALYZED OLEF IN METATHESIS 647
ABBREVIATIONS 659
REFERENCES 661
Index 670