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PHOSPHORUSCHEMISTRY. BIOCHEMISTRY AND TECHNOLOGY
SIXTH EDITION
D.E.C. CORBRIDGE
/0\ CRC Press\C/*" J Taylor &Francis Group
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Croup, an Informa business
Contents
Preface XXX1
Acknowledgements xxxiii
Chapter 1 Introduction and Historical Background 1
1.1 General Overview 1
1.2 Historical Survey 2
1.2.1 Importance of Phosphorus Compounds 5
1.3 Classification and Nomenclature of P Compounds 14
1.3.1 Formulae and Graphics 21
1.4 Literature of Phosphorus Chemistry 21
Bibliography 22
Chapter 2 Distribution and Environment 23
2.1 General Occurrence 23
2.2 Phosphate Mineral Deposits 25
2.2.1 Apatitic Phosphate Minerals CaiotPO^MF.OH.Cl), 25
2.2.2 Non-Apatitic Phosphate Minerals 27
2.2.3 Apatite Mining Development 28
2.2.4 Production and Reserves 29
2.2.5 Alternative Sources of Phosphorus 31
2.2.6 Active Biosources of Phosphorus 31
2.2.7 Extra-Terrestrial Phosphorus and Reduced Forms 33
2.3 Environmental Phosphorus 34
2.3.1 Natural and Artificial Cycles of Phosphorus 34
2.3.2 Ocean Phosphate 35
2.3.3 Phosphate in Lakes and Rivers 37
2.3.4 Phosphorus Content of Road-Deposited Sediments 37
2.3.5 Phosphorus Content of Desert Dusts 37
2.3.6 Planetary Distribution of Apatite 37
2.3.7 Eutrophication and Pollution 38
2.3.8 Sewage Treatment 39
2.3.9 Future Ecological Outlook 39
2.3.10 Toxicity of Phosphorus Compounds 40
2.3.11 Possible Radioactivity and Other Hazards 40
References 41
Chapter 3 Atomic and Molecular Properties 45
3.1 Atomic Properties 45
3.1.1 Comparisons with Pnictides 46
3.1.2 Electronegativity 47
3.1.3 Electron Affinity 48
3.1.4 Ionization Potential 49
3.1.5 Basic Stereochemistry 49
vii
v;jj Contents
3.1.6 Oxidation States 51
3.1.7 Electronic Structure 52
3.1.8 Formal Valence Bond Structures 54
3.1.9 BondOrbitals 55
3.1.10 Basic Schemes of c-Bonding (Single Bonds) 57
3.1.11 djt~p7i Bonding 59
3.1.12 pjt-prc Bonding 61
3.1.13 Metal-Phosphorus and dic-drc Bonding 62
3.1.14 Mixed Valency Compounds 64
3.2 Equilibria and Stereochemistry 64
3.2.1 Optical Isomers 64
3.2.2 Inversion and Pseudorotation 65
3.2.3 Fluxional Molecules 66
3.2.4 Tautomerism 66
3.2.5 Equilibria of Trigonal Bipyramidal Molecules 67
3.2.6 Resonance (Mesomerism) 67
3.2.7 Sigmatropic Rearrangements: Phospha-Cope 68
3.2.8 Reorganisation Reactions 69
3.3 Types of Reaction 70
3.3.1 Phosphorylation 74
3.3.2 Ester Hydrolysis Involving P-O-P or P-O-C Linkages 76
3.3.3 Thermal Condensation 77
. 3.3.4 Oxidation 77
3.3.5 Reduction 77
3.3.6 Michaelis-Arbusov Reaction (Arbusov Reaction) 78
3.3.7 Wittig Reaction 78
3.3.8 Kirsanov Reaction 79
3.3.9 Polymerisations 79
3.4 Bond Strengths and Bond Lengths 80
3.4.1 Bond Strengths 80
3.4.2 Covalent Bond Lengths and Interatomic Distances 82
3.4.3 Long Bonds 87
References 90
Chapter 4 Phosphides of Non-Metals 93
4.1 The Element 93
4.1.1 White Phosphorus 93
4.1.2 By-Products from Apatite 95
4.1.3 Alternative Processes for Extraction of Phosphorus from Its Ores.. 95
4.1.4 Properties of White Phosphorus 96
4.1.5 Black Phosphorus 99
4.1.6 Cubic Black Phosphorus and Rhombohedral Black Phosphorus.. 100
4.1.7 Phosphorus Nanotubes 101
4.1.8 Red Phosphorus 101
4.1.9 Commercial Red Phosphorus 102
4.1.10 Phosphorus Vapour 105
4.1.11 Liquid Phosphorus 105
4.1.12 Phosphohedrane Structures 105
4.1.13 Phosphorus Anions 108
4.1.14 Phosphorus Cations 110
Contents [X
4.1.15 Comparisons of Pnictide Elements 110
4.1.16 Interpnictide Compounds Ill
4.2 Oxides 113
4.2.1 Phosphorus Pentoxide (Phosphoric Anhydride) 113
4.2.2 Phosphorus Trioxide 118
4.2.3 Phosphorus Tetroxide 119
4.2.4 Sub-Oxides of Phosphorus 120
4.2.5 Miscellaneous Oxides 121
4.2.6 Pnictide Oxide Comparisons 121
4.3 Sulphides 122
4.3.1 Thermal Stability of Phosphorus Sulphides 127
4.3.2 Hydrolytic Stability of Phosphorus Sulphides 127
4.3.3 Oxysulphides of Phosphorus 131
4.4 Hydrides 132
4.4.1 Pnictide Hydrides, XH3 134
4.4.2 Phosphine, PH3 134
4.4.3 Phosphonium Salts 138
4.4.4 Phosphide Anion, PHj 138
4.4.5 Phosphinidene, PH 138
4.4.6 Diphosphine 138
4.4.7 Polyphosphines 140
4.4.8 Triphosphine 140
4.5 Nitrides 143
4.5.1 Phosphazate Anions, [PrNJ"-17a 145
4.6 Halides 146
4.6.1 Phosphorus Trihalides 146
4.6.2 Phosphorus Pentahalides 152
4.6.3 Mixed Pentahalides 156
4.6.4 Polyhalides of Phosphorus 159
4.6.5 Polyphosphorus Halides 159
4.6.6 Hexahalophosphates (Halophosphorides) 160
4.6.7 Addition Complexes 162
4.6.8 Pseudo Halides 163
4.6.9 Phosphoryl Halides (Phosphorus Oxyhalides) 163
4.6.10 Phosphoryl Halide Complexes 166
4.7 Borides 167
4.8 Carbides 169
4.9 Silicides 170
References 170
Chapter 5 Oxyphosphorus Compounds 177
5.1 Introduction 177
5.2 Phosphoric and Polyphosphate Acids 179
5.2.1 The Commercial Wet Process 179
5.2.2 By-Products from the Wet Process 181
5.2.3 Alternative Processes for Phosphoric Acid Manufacture 182
5.2.4 Properties of Orthophosphoric Acid (H3P04) L&3
5.2.5 Deuterophosphoric Acid 187
5.2.6 Polyphosphoric Acids 187
5.2.7 Pyrophosphoric Acid 188
x Contents
5.2.8 Triphosphoric Acid 189
5.2.9 Metaphosphoric Acid 189
5.2.10 Commercial Superphosphoric Acid 189
5.2.11 Commercial Polyphosphoric Acid 190
5.3 Orthophosphates 190
5.3.1 General Properties 190
5.3.2 Alkali Metal Orthophosphates 191
5.3.3 Ammonium Phosphates 194
5.3.4 Alkaline Earth Orthophosphates 196
5.3.5 Apatites (Fluorapatite and Hydroxyapatite) 197
5.3.6 Monocalcium Phosphate (Ca(H2P04)2) and Dicalcium
Phosphate (CaHP04) 202
5.3.7 Octacalcium Phosphate (Ca8H2(P04)6 • 5H20) 203
5.3.8 Tetracalcium Phosphate (Ca4P209) 203
5.3.9 Tricalcium Phosphate (Ca3(P04)2) 203
5.3.10 Amorphous Tricalcium Phosphate 204
5.3.11 Applications of Calcium Orthophosphates 204
5.3.12 Silica-Type Phosphates 205
5.3.13 Ionic Phosphates of Iron, Aluminium and Manganese 207
5.3.14 Aluminium Phosphates 208
5.3.15 Iron Phosphates 210
5.3.16 Manganese Phosphates 211
5.3.17 Chromium Phosphates 211
5.3.18 Zinc Phosphates 213
5.3.19 Copper Phosphates 213
5.3.20 Silver Phosphate 214
5.3.21 Lead Orthophosphates 214
5.3.22 Heavy Metal Phosphates 214
5.3.23 Mixed-Calion Orthophosphates 216
5.3.24 Mixed-Anion Salts 218
5.3.25 Phosphate Minerals as Gemstones 219
5.3.26 Complex Phosphate Salts 219
5.4 Condensed Phosphates 219
5.4.1 Linear Polyphosphates, P,^"'" 222
5.4.2 Pyrophosphates (n = 2) 222
5.4.3 Mixed-Metal Pyrophosphates 228
5.4.4 Triphosphates (« = 3) 229
5.4.5 Tetraphosphates (w = 4) 232
5.4.6 Pentaphosphates (n = 5) 233
5.4.7 Oligophosphates (n = -6-50) 233
5.4.8 Long-Chain Polyphosphates (« = 50) 234
5.4.9 Solution Properties of Linear Polyphosphates 237
5.4.10 Metaphosphates 240
5.4.11 Trimetaphosphates (n = 3) 241
5.4.12 Tetrametaphosphates 242
5.4.13 Larger Metaphosphate Rings (n > 4) 244
5.4.14 General Properties of Cyclic Metaphosphates 245
5.4.15 Ultraphosphates 247
5.4.16 Mixed-Anion and Mixed-Cation Condensed Phosphates 250
5.4.17 Isostructural Condensed Anions 250
5.4.18 Mixed Condensed Tetrahedral Oxyanions 252
Contents
5.4.19 Arsenatophosphates 253
5.4.20 Sulphatophosphates 254
5.4.21 Chromatophosphates 254
5.4.22 Silicophosphates 254
5.4.23 Borophosphates and Stannophosphates 255
5.5 Substituted Phosphates 255
5.5.1 Lower Oxo-Acids 256
5.5.1.1 Phosphorous Acid 256
5.5.1.2 Hypophosphorous Acid 259
5.5.2 Blaser and Worms Nomenclature 264
5.5.3 Miscellaneous Oxo-Acids 264
5.5.4 Peroxophosphates and Peroxyhydrates 266
5.5.4.1 Perdiphosphoric Acid 266
5.5.5 Halogeno Oxyacids 267
5.5.5.1 Phosphorodifluoridic Acid 268
5.6 Phosphate Esters 270
5.6.1 Preparation of Orthophosphate Esters 271
5.6.2 Preparation of Pyrophosphate Esters 273
5.6.3 Preparation of Polyphosphate and Metaphosphate Esters 275
5.6.4 Esters of Lower Phosphorus Oxyacids 276
5.6.5 Halophosphates 277
5.6.6 Properties of Esters 277
5.6.7 Hydrolysis of Esters 281
5.7 Complex Phosphates and Space-Containing Structures 284
5.7.1 Types of Space-Containing Structures 285
5.7.2 Cavity Structures 285
5.7.3 Nanostructured Materials 285
5.7.4 Microporous Materials 286
5.7.5 Phosphates with Ion Vacancies ..289
5.7.6 Phosphates with Layer Structures 290
5.7.7 Polyoxometallates 293
5.7.8 Complex Structures with Oxides of Mo, W, V, Nb, Ta, Ti 293
5.7.9 Molybdophosphates 294
5.7.10 Vanadatophosphates 295
5.7.11 Niobiophosphates 296
5.7.12 Titanophosphates 296
5.7.13 Antimonophosphates 296
5.7.14 Heteropoly Acids and Their Salts 296
5.7.15 Complex Acid Phosphates with Metal-Metal Bonds 300
5.7.16 Di-Oxygen Complexes 301
5.7.17 Higher-Molecular-Weight Polyoxometallate Anions 301
5.7.18 Organic Templates 302
5.7.19 Phosphonate Polyoxometallates 303
5.7.20 Phosphonate Layer Structures 303
5.7.21 Pillared Layer Structures 304
5.7.22 Silicophosphates 307
5.7.23 Silicate Analogues 308
5.7.24 Phosphite Structures 312
5.7.25 Large-Pore Phosphate Structures 312
5.7.26 Oxynitrides and Nitridophosphates 313
5.7.27 Na-P-O-N Glasses 314
xjj Contents
5.7.28 Al-P-O-N Powders 314
5.7.29 Phosphorus Derivatives of Large Organic Molecules
with Cavities 314
References 316
Chapter 6 Carbophosphorus Compounds 327
6.1 Introduction and Nomenclature 327
6.1.1 Carbophosphanes P-C 328
6.1.2 Carbophosphenes P=C 329
6.1.3 Carbophosphynes P=C 329
6.1.4 Carbophosphorus Anions 330
6.1.5 Phosphane Nomenclature 331
6.1.6 Phosphene and Phosphyne Nomenclature 332
6.1.7 Formation of P-C Linkages 332
6.2 Phosphines 336
6.2.1 Preparation of Phosphines 338
6.2.2 Reactions of Phosphines 341
6.3 Phosphine Oxides 346
6.3.1 Reactions of Phosphine Oxides 347
6.3.2 Phosphine Peroxides 349
6.4 Phosphonous and Phosphinous Halides 350
6.5 Phosphonic and Phosphinic Halides 355
6.6 Phosphonous and Phosphinous Acids 357
6.6.1 Phosphonous Esters 358
6.6.2 Phosphinous Esters 361
6.7 Phosphonic and Phosphinic Acids 362
6.7.1 Primary Phosphinic Acids and Esters 362
6.7.2 Secondary Phosphinic Acids and Esters 363
6.7.3 Phosphonic Acids and Esters 364
6.7.4 Arbusov Reaction 365
6.7.5 Michaelis Reaction 366
6.7.6 Dialkyl Phosphonates 367
6.7.7 Acyl Phosphonates 368
6.7.8 Phospho-Aldol Reaction 369
6.7.9 Applications of Phosphonates: Phosphonate Layer Structures 369
6.8 Phosphites 370
6.8.1 Preparation of Phosphites 371
6.8.2 Abramov Reaction 375
6.8.3 Perkow Reaction 376
6.8.4 Dialkyl Phosphites 376
6.8.5 Applications of Organophosphites 377
6.9 Phosphonium Salts 378
6.9.1 Preparation of Phosphonium Salts 378
6.9.2 Properties of Phosphonium Salts 380
6.9.3 Applications of Phosphonium Salts 382
6.10 Phosphonium Ylids 383
6.10.1 Stability of Ylids 383
6.10.2 Wittig Reaction 385
6.10.3 Di-Ylids 387
6.10.4 Compounds with P-C-Metal Linkages 389
Contents*»'
6.10.5 Phosphoranylidene Phosphoranes 3916.10.6 Phosphonium Phosphides 3916.10.7 Phosphonium Phosphorides ('Onium-ate') 392
6.11 Carbenes and Carbanions 3926.12 Phosphoranes 394
6.12.1 Pentacarbophosphoranes 3946.12.2 Pentaoxyphosphoranes 3956.12.3 Mixed Phosphoranes 3966.12.4 Reactions of Phosphoranes 399
6.13 Phosphorides 4036.14 Compounds with One- and Two-Connected P Atoms 405
6.14.1 Phosphide Anions 4066.14.2 Phosphaalkynes 406
6.14.3 Phosphaalkenes 408
6.14.4 Phosphaketenes, RP=C=0 411
6.14.5 Phosphaallenes and Phosphabutatrienes 411
6.14.6 Phosphacarboimides 411
6.14.7 Phosphacyanins 412
6.14.8 Oxophosphines 412
6.14.9 Phosphinidenes R-P 413
6.15 Compounds with Three-Connected P Atoms 414
6.15.1 Phosphaalkynes 415
6.16 Cyaphides and Cyanides 417
6.17 Polyphosphines 420
6.17.1 Diphosphines 420
6.17.2 Polyphosphines 422
6.17.3 Multi-Ring and Cage Polyphosphines 427
6.17.4 Bis (Phosphines) and Poly (Phosphines) 428
6.17.5 Alkoxy and Aryloxy Diphosphines 431
6.18 Polyphosphonates and Polyphosphinates 433
6.19 Diphosphenes and Related Pv-P'" Compounds 4356.19.1 Phosphinoyl Phosphides 4386.19.2 Triphosphenium Cations 4386.19.3 Phosphapolyenes 439
6.19.4 Diphosphaallenes, RP=C=PR 4406.19.5 Diphosphabutadienes 440
6.19.6 Triphosphapentadienes 441
6.19.7 Phosphahexadienes 441
6.19.8 Diphosphaalkynes 442
6.19.9 Rings Based on Phosphorus and Carbon Atoms 442
6.20 Saturated Rings with Phosphorus and Carbon 443
6.20.1 Phosphorinanes 444
6.20.2 Phospholanes 446
6.20.3 Phosphetanes 447
6.20.4 Phosphiranes 449
6.20.5 Bi-Nuclear Compounds 449
6.20.6 Saturated Rings with Two or More P Atoms 450
6.20.7 Phosphorus-Substituted Sugar Rings 453
6.21 Unsaturated Rings with Phosphorus and Carbon 454
6.21.1 Aromaticity 455
6.21.2 Phosphinine 457
xjv Contents
6.21.3 Phospholes 457
6.21.4 Phospholide (Phospholyl) Anions 460
6.21.5 Phospholenes 461
6.21.6 Phosphetenes and Phosphetes 461
6.21.7 Phosphirenes 462
6.21.8 Trisphat Anions 465
6.21.9 Aza Derivatives 467
6.21.10 Large Rings Based on P and Acetylene Units 467
6.22 Condensed Rings and Cages with Phosphorus and Carbon 468
6.22.1 Cage Systems 471
6.22.2 Calixarene-Type Molecules 472
6.22.3 Very Small Cages 473
6.23 Rings and Cages with Phosphorus, Carbon and Oxygen 473
6.23.1 Cage Compounds 481
References 484
Chapter 7 Azaphosphorus Compounds 497
7.1 Nomenclature 497
7.1.1 Phosphazanes (Azaphosphanes) 497
7.1.2 Phosphazenes (Azaphosphenes) 501
7.1.3 Phosphazynes (Azaphosphynes) 502
7.1.4 The Phosphorus-Nitrogen Linkage 503
7.2 Compounds of Phosphorus, Nitrogen and Hydrogen 504
7.2.1 Compounds of P, N and H Only 504
7.3 Phosphazanes with P-NH Linkages 506
7.3.1 Condensed Amino Compounds 509
7.4 Phosphazanes with P-N-C Linkages 510
7.4.1 Halogen Compounds 513
7.4.2 Azaphosphenium Cations 517
7.4.3 Azaphosphonium Cations 517
7.4.4 Azaphosphoranes 518
7.4.5 Azaphosphorides 519
7.4.6 Diphosphenes 521
7.4.7 Imido Analogues of Phosphorus Oxyacids 522
7.5 Phosphazanes with P-N and P-C Linkages 523
7.5.1 Phosphonous and Phosphinous Amides 524
7.5.2 Azaphosphonium Salts 527
7.5.3 Azaphosphoranes 527
7.5.4 Azaphosphorides 528
7.6 Hydrazides and Azides 528
7.6.1 Hydrazides 528
7.6.2 Azides 530
7.7 Polymeric Phosphazanes and Cyclic Compounds 531
7.7.1 Imidodiphosphazanes 531
7.7.2 Diphosphazanes with P-P Bonds 532
7.7.3 Cyclodiphosphazanes 533
7.7.4 Cyclotriphosphazanes (Metaphosphimates)(Imidometaphosphates) 535
7.7.5 Cage and Complex Ring Phosphazanes 540
7.8 Cyclic Phosphazenes 547
Contents xv
7.8.1 Wholly Substituted Cyclic Derivatives 549
7.8.2 Cychdiphosphazenes 554
7.8.3 Bonding in Cyclic Phosphazenes 554
7.8.4 Partially Substituted Halides 556
7.8.5 Isomerism of Cyclic Derivatives 5577.8.6 Condensed and Multi-Ring Phosphazenes 560
7.8.7 Metallocyclophosphazenes 5637.9 Linear Phosphazenes 564
7.9.1 Very Basic Compounds 5667.10 Monophosphazenes 573
7.10.1 Methods of Preparation 5747.10.2 Silyl Iminophosphoranes 5787.10.3 Sulphur Iminophosphoranes 579
7.10.4 Hydrazino and Azo Derivatives 5807.10.5 Phosphazene-Phosphazane Transitions 580
7.11 Two- and Three-Connected Phosphazenes 5817.12 Phosphazynes 586References 588
Chapter 8 Metallophosphorus Compounds 593
8.1 Metal Phosphides: Introduction 5938.1.1 Preparation of Metal Phosphides 594
8.2 Metal-Rich Phosphides MA.PKX > Y 5988.2.1 Phosphides in Metallurgy 598
8.3 Ionic Phosphides-
6008.4 Phosphides with Complex Anions 6048.5 Monophosphides 6058.6 Phosphorus-Rich Phosphides 6088.7 Miscellaneous Phosphides 610
8.7.1 Ternary Phosphides 610
8.7.2 Quaternary Phosphides 612
8.7.3 Metal Phosphide Oxides 612
8.7.4 Metal Phosphide Halides 612
8.7.5 Metal Phosphide Sulphides 612
8.7.6 Metal Phosphide Nitrides 6'2
8.7.7 Metal Phosphide Borides 612
8.7.8 Metal Phosphide Carbides 612
8.7.9 Metaliophosphohedranes 612
8.8 Metallophosphines and Metallophosphites 6138.9 MetalJopbosphoms Coordination Complexes 617
8. (0 Complexes with M-P-C Bonds 618
8.10. i Preparation of Phosphine Complexes 619
8.10.2 Stereochemistry and Isomerism 620
8.10.3 Reactions of Complexes 622
8.10.4 Dinitrogen Complexes 626
8.10.5 CaKuplexas with. Bcid%itv% Groups 627
8.10.6 Carbon Dioxide Complexes 628
8.10.7 Hydrogen Complexes 628
8. J0.8 Polymer Formation 630
8.10.9 Phosphine Complexes with Metal-Metal Bonds 632
xvi Contents
8.10.10 Cluster Complexes 632
8.10.11 Phosphido Complexes 636
8.10.12 Phosphinidene Complexes 637
8.10.13 Poly(phosphine) Multidentate Ligands 638
8.10.14 Reversible Uptake of Gases 639
8.10.15 Pincer-Type Ligands 642
8.10.16 Tripod-Type Ligands 642
8.10.17 Macrocyclic Ligands 644
8.10.18 Non-Flexible Ligands 644
8.10.19 Complexes with Multiple Metal-Metal Linkages 645
8.11 Complexes with M-P-H Bonds 645
8.12 Complexes with M-P-Halogen Bonds 646
8.12.1 Phosphobridged Complexes 649
8.13 Complexes with P-M, P-0 and P-C Bonds 650
8.13.1 Preparation of Phosphite Complexes 650
8.13.2 Metal Cluster Phosphite Complexes 652
8.13.3 Orthophenylation Reactions 653
8.13.4 Phosphonite and Phosphinite Complexes 654
8.13.5 Phosphite Phosphonito and Phosphinito Complexes 654
8.13.6 Pyro Complexes 655
8.14 Bonding Effects in Metal Complexes 656
8.14.1 Trans Effects 658
8.15 Complexes with P-P Bonds 659
8.16 Complexes with P„ Units Bonded to M Atoms 661
8.17 Diphosphene and Phosphaalkene Complexes 669
8.17.1 R-P=P-R Compounds 669
8.17.2 Phosphaalkene RP=CR2 Complexes with P-Metal Linkages 672
8.17.3 Diphosphaallyl Complexes 673
8.17.4 Phosphaalkyne P=CR Complexes with P-Metal Linkages 673
8.18 Metallophosphene and Metallophosphyne Complexes 674
8.19 Metal Complexes of Cyclic P and C Compounds 676
8.19.1 Five- and Six-Membered Unsaturated Rings 676
8.19.2 Four-Membered Unsaturated Rings 680
8.19.3 Three-Membered Unsaturated Rings 681
8.19.4 Zirconium and Hafnium Complexes 682
8.20 Metal Complexes of P-N and P/N Compounds 684
8.20.1 Phosphazenes (Azaphosphenes) 685
8.20.2 Coordination by P/N Ligands 686
8.20.3 Phosphorane Iminato Complexes (Phosphinimide Complexes).... 6888.21 Polymers with Metal-Phosphorus Linkages 691
8.21.1 Metallophosphorus Polymers 691
8.21.2 Nanoparticle Polymers 694
8.22 Miscellaneous Complexes Containing P and M Atoms 694
8.22.1 Complexes with M-P-O, M-P-S and M-P-C Linkages 694
8.22.2 Polyphosphoxanes 695
8.22.3 Phospholide Complexes 696
8.22.4 Metallophosphorane Complexes 697
8.22.5 Complexes with M-P-Si Bonds 697
8.22.6 Complexes with M-P-B Bonds 698
8.22.6.1 Large Ring Complexes 698
References 698
Contents xvii
Chapter 9 Compounds with p-Block Elements 709
9.1 Phosphorus and Boron 709
9.1.1 Phosphine Boranes o'V 710
9.1.2 Phosphinoboranes (a3a3) 713
9.1.3 Boraphosphetanes 715
9.1.4 Ring and Cage Compounds 716
9.1.5 Borazine Analogues 717
9.1.6 Boraphosphenes 718
9.1.7 Boraphosphides 718
9.1.8 Phosphinidoboranes 719
9.1.9 Boron Cage Compounds 721
9.1.10 Phosphaboranes and Phosphacarboranes 724
9.1.11 Phosphine-Metal-Borane Cage Compounds 726
9.1.12 Compounds withP-O-B Linkages 728
9.2 Phosphorus and Aluminium 730
9.3 Phosphorus and Gallium 734
9.4 Phosphorus and Indium 735
9.4.1 Compounds with P-O-M Linkages, M = Al, Ga or In 735
9.5 Phosphorus and silicon 736
9.5.1 Silicophosphide Anions 739
9.5.2 Organosilaphosphorus Compounds 739
9.5.3 Organosilicophosphide Anions 743
9.5.4 Ring Compounds Based on Phosphorus and Silicon 744
9.5.5 Cage Compounds of Phosphorus and Silicon 747
9.5.6 Silaphosphenes 749
9.5.7 Compounds with Si-O-P Linkages 750
9.5.8 Silyl Phosphites, Phosphonites and Phosphinites 753
9.6 Phosphorus and Germanium 754
9.6.1 Germaphosphenes (Germylene Phosphines) 756
9.6.2 Compounds with Ge-O-P Linkages 756
9.7 Phosphorus and Tin 757
9.7.1 Stannaphosphenes (Stannylene Phosphines) 759
9.7.2 Compounds with Sn-O-P Linkages 759
9.8 Phosphorus and Lead 760
9.9 Phosphorus and Arsenic, Antimony or Bismuth 761
9.10 Phosphorus and Sulphur 765
9.10.1 Thiophosporyl Halides 766
9.10.1.1 Isocyanates and Isothiocyanates 767
9.10.2 Phosphorothioic Acids 767
9.10.2.1 Phosphorotetrathioates 768
9.10.2.2 Preparation of O-S Esters 772
9.10.3 Phosphine Sulphides 772
9.10.4 Thioated Oxyacids 774
9.10.4.1 Phosphinothious Acids and Esters 775
9.10.4.2 Phosphonothionic and Phosphinothionic Halides 775
9.10.4.3 Phosphinothioic and Phosphonothioic Acids 776
9.10.4.4 Phosphonothious and Phosphorothious Acids 780
9.10.4.5 Mixed Phosphono and Phosphino Acids 781
9.10.5 Thiophosphonium Salts 784
9.10.6 Condensed Phosphoro, Phosphono and Phosphinothioates 784
xviii Contents
9.10.7 Compounds with P-S and P-N Linkages 791
9.10.7.1 Ring and Cage Compounds Based on P, S and N 793
9.10.8 Polyphosphorus Compounds with P-S and P-C Linkages 795
9.10.8.1 Metal-Thio Complexes with M-S-P Linkages 799
9.10.8.2 Ring Compounds with P and S 802
9.10.8.3 Ring Compounds with P, S and C 803
9.10.9 Low-Coordinated Compounds with P-S Linkages 805
9.10.9.1 Dithiooxophosphoranes 805
9.10.9.2 Thioxophosphines 806
9.10.9.3 Thiometaphosphate Anions 807
9.10.9.4 Iminothioxo, Phosphinylidenethioxo and
Methylenethioxophosphoranes 807
9.10.9.5 Thiaphosphenium Cations 808
9.10.9.6 Six-Coordinated Thiaphosphorus Compounds 808
9.11 Phosphorus and Selenium or Tellurium 808
9.11.1 Selenophosphoryl Halides 810
9.11.2 Tertiary Phosphine Selenides 810
9.11.3 Organohalides and Esters 811
9.11.4 Seleno Acids 811
9.11.5 Seleno Derivatives with Two or More P Atoms 812
9.11.6 Selenopyrophosphates (Selenodiphosphates) 813
9.11.7 Phosphorus Selenide Anions 813
9.11.8 Complexes with P-Se-M Linkages 813
9.11.9 Tellurium Complexes 815
9.11.10 Selenium Compounds with Low Phosphorus Coordination 817
9.11.11 Ring Compounds with P, Se and C Atoms 817
9.11.12 Ring Compounds with P, Se and In Atoms 818
9.11.13 Ring Compounds with P, Se and N Atoms 818
References 819
apter 10 Biopolymers and Phospho-Bioassemblies 829
10.1 Polysaccharides 830
10.1.1 General Features of Saccharides 830
10.1.2 Phosphomonosaccharides 834
10.1.3 Branching Points for Polyphosphate Chains 835
10.1.4 Synthesis of Phosphomonosaccharides 835
10.1.5 Polysaccharides 836
10.1.6 Phosphorylated Polysaccharides 838
10.1.7 Sugar-Phosphate Chains 839
10.1.8 Cellulose 839
10.1.9 Starch 840
10.1.10 Amylose Phosphates 843
10.1.11 Gelling Biopolymers 844
10.1.12 Retrogradation 844
10.1.13 Cycloamyloses 846
10.1.14 Cycloamylose Phosphates 846
10.1.15 Cyclic Phosphate-Linked Oligosaccharides 847
10.1.16 Cyclofructose 847
10.1.17 Glycogen 848
10.1.18 Chitin and Chitosan 848
Contents xlx
10.1.19 Heparin 849
10.1.20 Plant and Microbial Gums 849
10.1.21 Triple Helices 849
10.1.22 Wood 85010.1.23 Impregnated Rattan Wood 851
10.1.24 Cyclitols [CH(OH)]„ 851
10.2 Proteins 85110.2.1 Elemental Composition 85210.2.2 Protein Primary Structure 852
10.2.3 Solubility and Zwitterion Structure 85510.2.4 Protein Alphabet 856
10.2.5 Protein Secondary Structure 857
10.2.6 Collagen 85910.2.7 Solubility Classification of Proteins 86010.2.8 Denaturation 862
10.2.9 Conjugated Proteins 862
10.2.10 Phosphoproteins 862
10.2.11 Casein Protein 863
10.2.12 Whey Proteins 864
10.2.13 Lactalbumin Phosphate 864
10.2.14 Ovalbumin 865
10.2.15 Vitellin 867
10.2.16 Iron Storage Proteins 867
10.3 Lipids 868
10.3.1 Phospholipids 869
10.3.2 Polar Nature and Emulsifying Properties 870
10.3.3 Liposomes 872
10.3.4 Plasmalogens 874
10.3.5 Sphingomyelins 874
10.3.6 Teichoic Acids and Poly(Alkylene Phosphates) 875
10.3.7 Phosphopolyprenols 878
10.3.8 Polyhydroxyalkanoates 879
10.4 Nucleic Acids and Nucleotides 879
10.4.1 Nucleic Acids (Polynucleotides) 880
10.4.1.1 Composition and Primary Structure 880
10.4.1.2 Polynucleotide Minor Bases 883
10.4.1.3 Hydrolysis of Polynucleotides 884
10.4.1.4 Laboratory Synthesis of Polynucleotides 885
10.4.1.5 Molecular Weights of Nucleic Acids 885
10.4.1.6 Secondary and Tertiary Structure of Nucleic Acids 885
10.4.1.7 Chain Conformation in Amorphous States 889
10.4.1.8 RNA Structure 890
10.4.1.9 Denaturation and Melting of DNA 890
10.4.1.10 Metal Ions 892
10.4.1.11 Water Molecules 893
10.4.2 Mononucleotides 893
10.4.3 Synthesis of Oligo and Polynucleotides 895
10.4.4 Properties of Oligo and Polynucleotides 897
10.4.4.1 Synthetic Single-Stranded Polynucleotides 897
10.4.4.2 Left-Handed DNA 897
10.4.4.3 Mis-Matched Bases 898
xx Contents
10.4.4.4 Bonding and Oligonucleotide Configuration 899
10.4.4.5 Triple Helices and Alternative H-Bonding Schemes ....900
10.4.4.6 H-DNA 901
10.4.4.7 Quadruple Helices 901
10.4.4.8 Metal-Linked Oligonucleotides 902
10.4.4.9 Hoiliday Junctions 903
10.4.5 Modified Polynucleotides 903
10.4.5.1 Unnatural a-Isomers 903
10.4.5.2 Hexose Polynucleotides 904
10.4.5.3 Biological and Medical Objectives 904
10.4.5.4 Polyphosphate Polynucleotides: SpeculativeStructures 905
10.4.5.5 PolyADP-Ribose 907
10.4.5.6 Chemically Substituted Polynucleotides 907
10.4.5.7 Expanded DNA 908
10.4.5.8 PNA and TNA 908
10.4.5.9 Pseudo Polynucleotides 909
10.4.5.10 Polynucleotides Devoid of Sugar Rings 909
10.4.6 Nucleoside Polyphosphates 909
10.4.6.1 Nucleoside Polyphosphates 909
10.4.6.2 Adenosine-5'-Triphosphate 910
10.4.6.3 Nucleoside Diphosphates 912
10.4.6.4 Nucleoside Triphosphates and Higher Phosphates 914
10.4.6.5 Imido Triphosphates 915
10.4.6.6 Thioated Nucleotides 915
References 916
Chapter 11 Biophosphorus Chemistry 921
11.1 Body Composition and General Biochemical Background 921
11.1.1 Bones and Teeth 924
11.1.2 Pathological Calcification 926
11.1.3 Blood 926
11.1.4 Plasma Lipoproteins 928
11.1.5 Saliva 928
11.1.6 Muscle 929
11.1.7 Brain Tissue 929
11.1.8 Membranes 929
11.1.9 Ion Channels 931
11.1.10 Speculative Artificial Ion Channels 931
11.1.11 Mucosal Surfaces 931
11.1.12 Non-Membrane Cellular Phospholipids 931
11.1.13 Urine 932
11.2 Nutritional Aspects of Phosphorus 933
11.2.1 General Metabolism of Phosphorus and Calcium 933
11.2.2 Phosphorus Nutrition 934
11.2.3 Classes of Nutrients 935
11.2.4 Biosynthesis of Food 936
11.2.5 Vitamins 937
11.2.6 Distribution of Nutrients 93711.3 Energy Carriers 938
Contents xxi
11.3.1 Adenosine Triphosphate (ATP) 940
11.3.2 Coenzyme A 941
11.3.3 Nicotinamide Energy Carriers 942
11.3.4 Flavin Adenine Dinucleotide 942
11.3.5 Nucleoside Triphosphates 943
11.4 Enzymes 944
11.4.1 Nature of Enzymes 944
11.4.2 Enzyme Systems 945
11.4.3 Enzyme Efficiency 945
11.4.4 Classification of Enzymes 946
11.4.4.1 Hydrolases 947
11.4.4.2 Isomerases 948
11.4.4.3 Transferases and Phosphorylation 948
11.4.4.4 Oxidoreductases 950
11.4.4.5 Lyases 950
11.4.4.6 Ligases 950
11.4.5 Non-Enzymatic Reactions 951
11.4.6 Protein Phosphorylation 951
11.4.7 Phosphatase Test 952
11.4.8 Phosphoprotein Enzymes 952
11.5 Essential Bioprocesses 953
11.5.1 Energy Storage and Release 953
11.5.2 Photosynthesis 956
11.5.3 Glycogenesis 958
11.5.4 Phosphorolysis 959
11.5.5 Glucose Oxidation 959
11.5.6 Energy Yield from Glucose Oxidation 962
11.5.7 Pentose Phosphate Pathway 963
11.5.8 Gluconeogenesis 964
11.5.9 Nitrogen Fixation 965
11.5.10 Urea Cycle 966
11.5.11 Biosynthesis of Energy Carriers 967
11.5.12 Nerve Cells and Brain Function 969
11.5.13 Second Messengers 970
11.5.14 Muscle Action 971
11.5.15 Amino Acid Biosynthesis 972
11.5.16 GABA Synthesis 973
11.5.17 Fat Breakdown 974
11.5.18 Fatty Acid Synthesis 974
11.5.19 Sulphate Metabolism 977
11.5.20 The Sodium/Potassium Pump 978
11.5.21 Bioluminescence 978
11.5.22 Vitamins and Coenzymes 979
11.5.23 Terpenes and Related Compounds 980
11.5.24 Polysaccharide Synthesis with Polyprenols 982
11.6 Polynucleotide Functions 983
11.6.1 Hydrolysis of Polynucleotides 983
11.6.2 Chromosomes and Heredity 985
11.6.3 Histones and Nucleosomes 985
11.6.4 Ribosomes 986
11.6.5 Eukaryotic Genes 987
(Xjj Contents
11.6.6 Polynucleotide Biosynthesis 987
11.6.7 Biofunctions of RNA 990
11.6.8 RNA World 990
11.6.9 Transmission of Genetic Information 990
11.6.9.1 Replication 990
11.6.9.2 Transcription 993
11.6.9.3 Translation 994
11.6.10 Genetic Code 995
11.6.11 Mutagenesis and Errors in Transcription 995
11.6.12 Interaction of Foreign Substances with DNA 997
11.6.13 Binding of Foreign Molecules 997
11.6.14 DNA Methylation 998
11.6.15 Replication Errors 999
11.6.16 Telomeres and Apoptosis 1000
11.6.17 Oligonucleotide Drugs 1001
11.6.18 Micro-RNA 1002
11.6.19 Genetic Engineering (Cloning) 1002
11.6.20 Polymerase Chain Reaction 1004
11.6.21 Human Genome Project 1004
11.6.22 Human Cloning Projects 1004
11.6.23 Gene Therapy 1005
11.6.24 DNA 'Fingerprinting' 1005
11.6.25 Agricultural Applications 1005
11.6.26 DNA Microarrays 1005
11.6.27 Electromagnetic, Electronic and Related Properties of DNA 1005
11.6.28 Molecular Glue 1006
11.6.29 DNA as a Constructional Material 1006
11.6.30 Miscellaneous Recent Investigations 1006
11.6.31 Bacteria and Antibiotics 1007
11.6.32 Viruses 1008
11.6.33 Chemotherapy 1011
11.7 Phosphonate Metabolism 1012
References 1014
Chapter 12 Applications of Phosphorus Compounds 1021
12.1 Phosphoric Acid 1021
12.1.1 Attack of Phosphoric Acid on Metals 1022
12.1.2 Attack of Phosphoric Acid on Oxides 1023
12.1.3 Attack of Phosphoric Acid on Plastics 1023
12.1.4 Electrical Applications 1023
12.1.5 Miscellaneous Applications 1024
12.1.6 Calcium Phosphates 1024
12.1.7 Sodium Salts 1025
12.1.8 Potassium, Ammonium and Magnesium Salts 1025
12.1.9 Aluminium Salts 1025
12.2 Fertilisers 1025
12.2.1 Economics and Sociology of Fertilisers 1025
12.2.2 Nutritional Requirements in Agriculture 1026
12.2.3 Efficiency and General Fertiliser Practice 1027
12.2.4 Foliar Fertilisers 1028
Contents xxiii
12.2.5 Phosphatic Fertilisers 1028
12.2.6 Superphosphate Fertilisers 1029
12.2.7 Ammonium Phosphate Fertilisers 1030
12.2.8 Alternative Fertilisers 1030
12.2.9 Insoluble Slow-Acting Fertilisers 1031
12.2.10 Commercial Fertiliser Specification 1032
12.2.10.1 Fertiliser-Soil-Plant Interactions 1033
12.2.10.2 Synergistic Effects of Nutrients 1037
12.2.11 General Ecological Problems 1037
12.2.12 Hydroponics 1037
12.3 Animal Foodstuffs 1038
12.3.1 Animal Metabolism 1038
12.3.2 Dietary Requirements 1038
12.3.3 Animal Feed Contents 1039
12.4 Food Technology 1039
12.4.1 Milk and Dairy Products 104!
12.4.1.1 Milk Composition 1041
12.4.1.2 Phosphates as Milk Additives 1045
12.4.1.3 Cheese 1046
12.4.1.4 Butter and Margarine 1046
12.4.1.5 Eggs 1047
12.4.2 Meat and Fish 1049
12.4.2.1 Applications in Meat Technology 1050
12.4.3 Fruit and Vegetables 1051
12.4.4 Beverages 1051
12.4.5 Cereals and Related Products 1052
12.4.6 Leavening Agents 1053
12.4.7 Biopolymer Phosphates 1054
12.4.7.1 Polysaccharides 1054
12.4.7.2 Phosphoproteins 1055
12.4.7.3 Phospholipids 1056
12.4.7.4 Polynucleotides 1056
12.4.8 Miscellaneous Uses 1056
12.5 Detergents 1057
12.5.1 Soap 1057
12.5.2 Auxiliary Detergent Functions 1057
12.5.3 Detergent Powders 1058
12.5.4 Detergent Phosphates and Pollution 1058
12.5.5 Detergent Formulations 1058
12.5.6 Liquid Detergents 1060
12.5.7 Special Detergents 1060
12.5.8 Metal Cleaning 1061
12.5.9 Textile Scouring and Bleaching 1062
12.6 Water Treatment 1062
12.6.1 Oligopolyphosphates 1063
12.7 Metal Surface Treatment 1064
12.7.1 Phosphating 1064
12.7.2 Phosphating of Iron and Steel 1065
12.7.3 Phosphating of Zinc or Galvanised Steel 1066
12.7.4 Manganese Phosphate Coatings 1067
12.7.5 Phosphating of Aluminium 1067
12.7.6 Alternative Phosphate Films 1068
12.7.7 Phosphate Films Modified by Organic Compounds 1069
12.7.8 Etch Primers 1069
12.7.9 Anti-Corrosive Paints 1069
12.7.10 Anodising 1°70
12.7.11 Chemical Polishing '°70
12.7.12 Electropolishing '071
12.7.13 Electroplating 1071
12.7.14 Electroless Plating 1Q72
12.7.15 Electrodeposition of Amorphous Alloys 1073
12.7.16 Super-Black Surfaces 1074
12.8 Pigments and Dyestuffs 1074
12.8.1 Coloured Inorganic Phosphate Pigments 1074
12.8.2 Dyestuffs and Organic Pigments 1075
12.9 Glasses 1078
12.9.1 Phosphate Glass Structure 1078
12.9.2 Graham's Salt 1079
12.9.3 Phosphate/Silicate, Phosphale/Arsenate and
Phosphate/Sulphate Glasses 1080
12.9.4 Soluble Glasses 1081
12.9.5 Insoluble Glasses 1082
12.9.6 Electrically Conducting Glasses 1083
12.9.7 Optical Glasses 1084
12.9.8 Coloured Glasses 1084
12.9.9 Oxy-Nitride Glasses 1084
12.9.10 Mechanical Strengthening by Phosphates 1085
12.9.11 Opalescence and Glass Ceramics 1085
12.9.12 Polymer Melt-Blend Glasses 1085
12.9.13 Glass-Ceramic Microspheres 1085
12.9.14 Bone China 1086
12.9.15 Glass Coatings 1086
12.9.16 Later Developments 1087
12.9.17 Metallic Glasses 1087
12.9.18 Phosphorus Sulphide/Selenide Glasses 1087
12.9.19 Oxynitride Glasses 1087
12.10 Phosphoceramic Constructional Materials 1087
12.10.1 Phosphate Bonding 1088
12.10.2 Cold-Setting Cements 1089
12.10.3 Reactions above Room Temperature 1090
12.10.4 Low-Expansion Ceramic Materials 1091
12.10.5 Phosphates and Portland Cement 1092
12.10.6 Miscellaneous Useful Materials 1092
12.10.7 Phosphogypsum 1093
12.11 Industrial Phosphate Esters 1094
12.11.1 Complex Formation and Metal Extraction 1095
12.11.2 Plasticisers and Flame Retardants 1097
12.11.3 Phosphate Ester Polymers 1098
12.11.4 Miscellaneous Applications of Phosphate Esters 1100
12.11.5 Phosphorothioate (Thiophosphate) Esters 1102
12.12 Pesticides 1103
12.12.1 Insecticides 1103
12.12.2 Environmental Hazards 1106
12.12.3 Wei 1-Known Insecticides 1107
12.12.4 Acaricides H10
12.12.5 Nematicides 1110
12.12.6 Structure-Activity Relationship 1110
12.12.7 Herbicides HU
12.12.8 Fungicides 1113
12.12.9 Rodenticides, Fumigants, Repellents and So On 1113
12.12.10 Chemosterilants 1114
12.12.11 Crop Improvement Agrochemicals 1114
12.12.12 Overall Crop Protection and Ultimate Food Consumption 1114
12.13 Medicinal Compounds and Toxic Esters 1115
12.13.1 Inorganic Phosphorus Compounds 1115
12.13.2 Phosphate Salts of Organic Drugs 1117
12.13.3 Pharmaceutical Organic Compounds 1118
12.13.4 Chemotherapy 1118
12.13.5 Drug Action 1119
12.13.6 Bone Resorption, Imaging and Bis-Phosphonates 1119
12.13.7 Radioprotective Agents 1120
12.13.8 Carcinostatic and Anti-Arthritic Drugs 1120
12.13.9 Anti-Viral Drugs 1121
12.13.10 Brain Disorders 1124
12.13.11 Phosphazenes 1124
12.13.12 Casein Products 1125
12.13.13 Phospholipids and Liposomes 1125
12.13.14 Aquasomes 1126
12.13.15 Vitamin Phosphate Esters 1126
12.13.16 Gene Therapy 1126
12.13.17 Medical and Biochemical Applications of Phosphorus NMR 1127
12.13.17.1 Magnetic Resonance Imaging 1127
12.13.17.2 Magnetic Resonance Spectroscopy 1128
12.13.18 Radioactive Phosphorus Compounds 1128
12.13.19 Nerve Gases 1128
12.13.20 Toxicity Assessment 1131
12.13.21 Antidotes 1131
12.13.22 Decontamination 1132
12.13.23 Detection H32
12.13.24 Miscellaneous Military Uses for Phosphorous Compounds 1132
12.14 Dental and Medical Materials 1133
12.14.1 Toothpastes 1133
12.14.2 Tooth Fillings 1134
12.14.3 Dental Investment Materials 1136
12.14.4 Bone Substitutes and Implant Materials 1136
12.14.5 Bone Cements 1138
12.14.6 Bioceramic Coatings U39
12.14.7 Processed Sea Coral 1139
12.14.8 Processed Rattan Wood 1139
12.14.9 Possible New Materials 1139
12.15 Synthetic Polymers and Fire Retardants 1139
12.15.1 Polymerised Phosphites 1142
12.15.2 Polymerised Phosphines 1143
xxvi Contents
12.15.3 Polymerised Phosphine Oxides H43
12.15.4 Polymerised Phosphinates U44
12.15.5 Reactions with Amides 1144
12.15.6 Group Transfer Alternating Polymers 1145
12.15.7 Phosphorus-Modified Polymers H45
12.15.8 Applications of Polymerised Phosphonates 1147
12.15.9 Artificial Glass 1147
12.15.10 Constructional Materials 1148
12.15.11 Ion Exchange Resins 1 '48
12.15.12 Anti-Oxidants 1148
12.15.13 Coupling Agents 1149
12.15.14 Fire Retardants and Flameproofing 1149
12.15.15 Liposomes and Phospholipids 1154
12.15.16 Highly Polymeric Phosphazenes H55
12.15.17 Dendritic Structures 1163
12.15.18 1 norganic Polyphosphate Fibres 1164
12.16 Pyrotechnics H65
12.16.1 Other Applications of Elemental Phosphorus 1166
12.16.2 Sea Flares 1167
12.17 Natural Products 1167
12.17.1 Casein 1167
12.17.1.1 Commercial 'Acid' Casein 1168
12.17.1.2 Rennet Casein 1168
12.17.1.3 Uses of Caseins 1169
12.17.1.4 Casein Glues 1169
12.17.1.5 Casein Plastics 1169
12.17.1.6 Casein Fibres 1169
12.17.1.7 Miscellaneous Applications of Casein 1169
12.17.2 Lecithin 1170
12.17.2.1 Uses for Lecithin 1171
12.17.3 Soya Milk 1173
12.17.4 Cereal Starches 1173
12.17.5 Phosphorylated Chitins and Chitosans 1173
12.17.6 Phosphorylated Natural Oils 1173
12.18 Catalysts and Synthetic Reagents 1173
12.18.1 Polyphosphoric Acid 1174
12.18.2 Phosphorus Pentoxide (Phosphoric Anhydride) 1175
12.18.3 Phosphorus Pentahalides 1176
12.18.4 Phosphorus Trihalides 1176
12.18.5 Phosphoryl Halides 1177
12.18.6 Hendrickson's Reagent 1177
12.18.7 HMPA 1177
12.18.8 Hypophosphorous Acid 1177
12.18.9 Organophosphites 1178
12.18.10 Organophosphines 1179
12.18.11 Triphenylphosphine + Carbon Tetrachloride 1179
12.18.12 Phosphoranes 1180
12.18.13 Tetraphosphorus Decasulphide (Phosphorus 'Pentasulphide') 1181
12.18.14 Lawesson's Reagent 1181
12.18.15 Aminating Agents 1181
12.18.16 Diethylcyanophosphonate 1181
Contents xxv"
12.18.17 Wittig Syntheses 1182
12.18.18 Mitsunobu Reaction 1183
12.18.19 Ring Closure Reactions 1183
12.18.20 Inorganic Phosphates 1184
12.18.21 Metallophosphorus Compounds 1185
12.18.22 Hydrogenation 1185
12.18.23 Hydroacylation 1186
12.18.24 Carbonylation 1186
12.18.25 Decarbonylation 1186
12.18.26 Hydroformylation 1186
12.18.27 Triphenylphosplune Copper Hydride 1187
12.18.28 Transfer Hydrogenation 1187
12.18.29 Hydrosiration 1188
12.18.30 Nitrogen Fixation 1188
12.18.31 Oxidation 1188
12.18.32 Hydrocyanation 1188
12.18.33 Hydrocarbon Coupling 1189
12.18.34 Heck Coupling and Kumada Coupling 1189
12.18.35 Ring Closure 1189
12.18.36 Reductive Coupling 1190
12.18.37 Isomerisations 1190
12.18.38 Isotope Exchange 1190
12.18.39 Polydentate Metal Complexes and Asymmetric Syntheses 1190
12.18.40 Water-Soluble Catalysts (Aqueous Biphasic Catalysts) 1194
12.18.41 Enanlioselective Organocatalysts 1194
12.18.42 Heterogeneous Catalysts 1195
12.19 Metallurgy and Metal Phosphides 1196
12.19.1 Structural Background of Metals 1197
12.19.2 Types of Lattice Substitution 1198
12.19.2.1 Substitutional Solid Solutions 1198
12.19.2.2 Interstitial Solid Solutions 1199
12.19.2.3 Lattice Vacancies: Effects on Composition 1200
12.19.3 Cast Iron and Steel 1200
12.19.4 Phosphides in Metallurgy 1202
12.19.4.1 Cast Iron 1203
12.19.4.2 Steel 1203
12.19.4.3 Phosphor Bronze 1205
12.19.4.4 Phosphor Copper 1206
12.19.5 Powder Metallurgy 1206
12.19.6 Vitreous Metals and High-Strength Alloys 1206
12.20 Electronic, Electrical and Related Materials 1207
12.20.1 Thin Film Production 1208
12.20.2 Light-Emitting Diodes 1209
12.20.3 Quantum Dots 1211
12.20.4 Superconductors 1212
12.20.5 Amorphous Glassy Phases 1213
12.20.6 Photoluminescence, Phosphorescent and
Fluorescent Materials 1213
12.20.7 Superionic Conductors 1215
12.20.8 NZP Structures 1215
12.20.9 Nasicon 1215
xxviii Contents
12.20.10 Re-Chargeable Lithium Ion Batteries 1217
12.20.11 Lithium Phosphate: Lithium Silicate System 1217
12.20.12 Cubic Trisodium Phosphate 1217
12.20.13 Non-Linear Optical Materials 1217
12.20.14 Laser Materials 1218
12.20.15 Thermoelectric Effects 1218
12.20.16 Piezoelectricity and Ferroelectricity 1219
12.20.17 Potassium Dihydrogen Phosphate 1219
12.20.18 Caesium Phosphates 1221
12.20.19 Magnetic Properties 1221
12.20.20 Colour Modification of Diamonds 1221
12.20.21 Nanostructured Materials 1221
12.20.22 Ionic Liquids 1222
12.20.23 DNA and Molecular Electronics 1222
References 1222
Chapter 13 Special Topics '245
13.1 Hydrogen Bonding 1245
13.1.1 Evidence for Hydrogen Bonding 1245
13.1.2 Classification of H Bonds 1246
13.1.3 Role of Hydrogen Bonds 1247
13.1.4 Liquid and Solution States 1248
13.1.5 Geometrical Features in Crystalline Compounds 1248
13.1.6 Proton Transfer 1253
13.1.7 Effects of H Bonding on Equilibria 1257
13.1.8 Short Hydrogen Bonds 1257
13.1.9 Hydrogen Bonds Involving Carbon 1260
13.1.10 Hydrogen Bonds Involving Fluorine 1261
13.1.11 Hydrogen Bonds Involving Sulphur 1261
13.1.12 Hydrogen Bonds Involving P-H Linkages 1262
13.2 Stereochemistry and Isomerism 1265
13.2.1 Optical Activity and Enantiomorphism 1265
13.2.2 Optical Resolution of Pyramidal Compounds 1267
13.2.3 Inversion of Pyramidal and X-V Tetrahedral
Compounds 1269
13.2.4 Preparation of Optically Active (Chiral) Phosphines 1271
13.2.5 Trigonal Bipyramidal and Octahedral Compounds 1273
13.2.6 Isomerism of Phosphaethynes and Diphosphenes 1274
13.2.7 Isomerism of Polyphosphine Derivatives 1276
13.2.8 Ring Isomerism 1278
13.2.9 Isomerism of Phosphosaccharides 1282
13.2.10 Isomerism of Polynucleotides 1283
13.2.11 Isomerism of Cyclophosphazenes 1283
13.3 Pseudorotation and the Trigonal Bipyramid 1283
13.3.1 Interconversion of Isomers 1285
13.3.2 Apicophilicity and BPR 1285
13.3.3 Interconversion of Mono and Bicyclic Phosphoranes 1288
13.3.4 Isomerism in Octahedral Spiro Compounds 1291
13.3.5 Reaction Paths with Phosphoranes 1291
13.4 Free Radicals and Short-Lived Species 1294
Contents xxix
13.4.1 Production of Free Radicals 1294
13.4.2 Non-Radical Species 1295
13.4.3 Mouometaphosphate Anions 1296
13.4.3.1 Phosphenites, (RO)-P = 0 1297
13.4.3.2 Phosphoranide Anions, R4P~ 1297
13.4.3.3 Phosphenium Cations, R2P+ 1297
13.4.4 Radical Species 1298
13.4.4.1 Phosphinyl Radicals, R2Pand (RO)2P 1298
13.4.4.2 Phosphonyl Radicals, R2PO and (RO)2PO 1300
13.4.4.3 Phosphoranyl Radicals, R4P and RP(OR), 1300
13.4.4.4 Phosphonium Radical Anions, R3P~
(Phosphine Radicals) 1304
13.4.4.5 Phosphinium Radical Cations, R_,P+ 1304
13.4.4.6 Phosphite and Hypophosphite Radicals, POj, HPOj -1304
13.4.5 Miscellaneous Radicals 1305
13.5 Radioactivity and Radiochemistry 1305
13.5.1 Medical and Biochemical Applications 1308
13.5.2 Ecological Studies 1309
13.5.3 Miscellaneous Uses 1309
13.5.4 Radiation and Fragmentation 1309
13.5.5 Radiation and Organic Phosphate Esters 1313
13.6 Migrations, Rearrangements and Other Reactions 1313
13.6.1 Migrations of H Atoms 1313
13.6.2 Migration of Groups or Atoms Other than H 1316
13.6.3 Polymerisation and Rearrangement in Compoundswith Multiple Bonds 1319
References 1324
Chapter 14 Analysis and Characterisation 1329
14.1 Chemical Methods 1329
14.1.1 Qualitative Chemical Analysis 1329
14.1.2 Spot Tests 1330
14.1.3 Lower Oxo-Salts 1330
14.1.4 Quantitative Chemical Analysis 1331
14.1.5 Quantitative Gravimetric Methods 1331
14.1.6 Volumetric Methods 1332
14.1.7 Condensed Phosphates 1332
14.1.8 Phosphine Estimation 1332
14.1.9 Organic Phosphorus Compound Analysis 1332
14.1.10 Detection and Estimation of Other Elements Using
Phosphorus Compounds 1333
14.2 Physical Methods 1334
14.2.1 Spectrophotometry Methods 1335
14.2.1.1 Molybdovanadophosphate Method 1336
14.2.1.2 Phosphomolybdenum Blue Method 1336
14.2.1.3 Molybdophosphate Lakes 1336
14.2.2 Emission Spectra 1337
14.2.2.1 Visible and UV 1337
14.2.3 UV Absorption Spectra 1339
xxx Contents
14.2.4 Electron Probe Microanalysis 1339
14.2.5 Radioactivation Analysis 1340
14.2.6 Autoradiography 1340
14.2.7 Mass Spectra 1341
14.2.8 Electron Spin Resonance Spectroscopy 1341
14.2.9 Chromatography 1341
14.2.9.1 Anion Exchange Gradient Method 1343
14.2.10 Gel Electrophoresis 1344
14.2.11 Fluorescence Spectrometry 1344
14.2.12 Infra-Red Spectra 1344
14.2.13 Nuclear Magnetic Resonance Spectra 1350
14.2.14 X-Ray Diffraction 1354
14.2.15 Electron Diffraction and Electron Microscopy 1355
14.2.16 Other Techniques 1355
14.3 Biopolymer Analysis 1355
14.3.1 Protein Analysis 1356
14.3.2 Nucleic Acid Analysis 1358
14.3.3 Polysaccharide Analysis 1359
14.3.4 Phospholipid Analysis 1360
References 1360
Appendix 1: Atomic Data for the Elements 1365
Appendix 2: Hazards of Phosphorus Compounds 1369
Appendix 3: Properties of White Phosphorus, P4 1373
Appendix 4: Properties of 'Red' Phosphorus, P„ 1375
Appendix 5: Properties of Phosphine, PH3 1377
Appendix 6: Properties of Orthophosphoric Acid, H3P04 1379
Appendix 7: Abbreviations and Symbols 1381
Appendix 8: Conversion Factors 1389
Appendix 9: Shortened Journal Nomenclature 1391
Index 1393
Author Index 1437
