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Comprehensive Inorganic Chemistry II

Comprehensive Inorganic Chemistry II

Jan Reedijk | Kenneth R. Poeppelmeier

(2013)

Additional Information

Abstract

Comprehensive Inorganic Chemistry II reviews and examines topics of relevance to today’s inorganic chemists. Covering more interdisciplinary and high impact areas, Comprehensive Inorganic Chemistry II includes biological inorganic chemistry, solid state chemistry, materials chemistry, and nanoscience. The work is designed to follow on, with a different viewpoint and format, from our 1973 work, Comprehensive Inorganic Chemistry, edited by Bailar, Emeléus, Nyholm, and Trotman-Dickenson, which has received over 2,000 citations. The new work will also complement other recent Elsevier works in this area, Comprehensive Coordination Chemistry and Comprehensive Organometallic Chemistry, to form a trio of works covering the whole of modern inorganic chemistry. Chapters are designed to provide a valuable, long-standing scientific resource for both advanced students new to an area and researchers who need further background or answers to a particular problem on the elements, their compounds, or applications. Chapters are written by teams of leading experts, under the guidance of the Volume Editors and the Editors-in-Chief. The articles are written at a level that allows undergraduate students to understand the material, while providing active researchers with a ready reference resource for information in the field. The chapters will not provide basic data on the elements, which is available from many sources (and the original work), but instead concentrate on applications of the elements and their compounds.

  • Provides a comprehensive review which serves to put many advances in perspective and allows the reader to make connections to related fields, such as: biological inorganic chemistry, materials chemistry, solid state chemistry and nanoscience
  • Inorganic chemistry is rapidly developing, which brings about the need for a reference resource such as this that summarise recent developments and simultaneously provide background information
  • Forms the new definitive source for researchers interested in elements and their applications; completely replacing the highly cited first edition, which published in 1973

Table of Contents

Section Title Page Action Price
Volume 1: Main-Group Elements, Including Noble Gases 4
Copyright 5
Editorial Board 6
Contributors 8
Contents 22
Preface 36
Volume Editor´s Introduction 38
Catenated Compounds (including rings, chains & clusters, but not multiply bonded systems) 40
Chapter 1.01: Catenated Compounds - Group 13 (Al, Ga, In, Tl) 40
Introduction 40
Chain and Ring Compounds with Direct E-E-Single Bonds 41
Synthesis and Structures of Compounds with Solitary E2-Units 41
Trieldihalides 41
E2R4 compounds 42
Synthetic pathways 42
Structural features 42
Thallium-thallium interactions 44
Bulky silanide derivatives 44
Cycloaddition products of ditrielenes 45
Lewis acidity - higher coordination numbers 45
Heteroleptic compounds 46
Synthesis and Structure of Compounds with E3-Units 50
Synthesis and Structure of Compounds with Higher En-Units 52
Subhalides 52
Nonhalide derivatives 53
Synthesis and Structure of Compounds with E-E Bonds 58
Polyhedral Cluster Compounds 61
Tetrahedral E4R4 Cluster Compounds and Derivatives 61
Synthesis and structures 61
Bonding 62
Reactivity 65
Higher [EnRn]x- Cluster Compounds 65
Aromaticity of [EnRn]x- Cluster Compounds 69
Element-Rich Cluster Compounds 71
Introduction 71
Aluminum Cluster Compounds 73
Gallium Cluster Compounds 75
Ga8, Ga9, and Ga10 clusters 75
Ga11 and Ga13 clusters 79
Ga16, Ga18, and Ga19 clusters 79
Ga22 clusters 79
Ga23 and higher clusters 81
Indium Cluster Compounds 83
Conclusion 83
References 84
Chapter 1.02: Catenated Silicon Compounds 90
Introduction 90
Hydrosilanes 91
Synthesis 92
Properties and Reactivity 93
Applications 93
Halohydrosilanes 93
Acyclic Chlorohydrosilanes 94
Acyclic Bromohydrosilanes 96
Acyclic Iodohydrosilanes 96
Acyclic Fluorohydrosilanes 97
Mixed Acyclic Halohydrosilanes 98
Cyclic Halohydrosilanes 98
Halosilanes 98
Acyclic Perchlorosilanes 99
Acyclic Perbromosilanes 100
Acyclic Periodosilanes 100
Acyclic Perfluorosilanes 100
Mixed Acyclic Perhalosilanes 100
Cyclic Perhalosilanes 101
Chalcogenosilanes 101
Si-O Compounds 101
Acyclic Si-O Compounds 101
Siloxenes 102
Si-S Compounds 102
Si-Se, Si-Te, and Si-Po Compounds 103
Silanes with Group-15 Substituents 103
Si-N Compounds 103
Acyclic Si-N Compounds 104
Cyclic Si-N Compounds 105
N-Heterocyclic Silylenes as Starting Material for Acyclic and Cyclic Silanes 106
N-Substituted Pentacoordinated Si Compounds 108
Si-P Compounds 110
Si-As, Si-Sb, and Si-Bi Compounds 111
Silanes with Other Group-14 Substituents Except Organic Groups 111
Silanes with Other Group-13 Substituents 112
Silanes and Group-1 and -2 Metals 112
Silanes and Transition Metals 112
Silanes and Lanthanoids and Actinoids 117
Conclusion 118
References 118
Chapter 1.03: Catenated Compounds - Group 14 (Ge, Sn, Pb) 122
Germanium 123
Introduction 123
Synthetic Methods 123
Reactivity of the Ge-Ge Bond 123
Structural Features of the Ge-Ge Bond 123
Digermanes 123
Synthesis by coupling 123
Synthesis by addition 124
Functionalized digermanes 126
Linear and Branched Oligogermanes 126
Trigermanes 126
Tetragermanes 127
Linear 127
Branched 127
Penta-, hexa-, and higher oligogermanes 127
Cyclogermanes 127
Cyclotrigermanes 127
Cyclotetragermanes 128
Cyclopenta- and -hexagermanes 129
Heterocyclogermanes 129
Germanium Cages 130
Germanium Clusters 131
Polygermanes 134
Tin 135
Introduction 135
Synthetic Methods 135
Reactivity of the Sn-Sn Bond 136
Structural Features of the Sn-Sn Bond 136
Di- and Oligostannanes 136
Condensation reactions 136
Wurtz-type coupling reactions and comparable methods 137
Derivatives of unsaturated organotin compounds 139
Di- and oligostannanes as part of transition-metal complexes 140
Derivatization of di- and oligostannanes 142
Formation of Sn-Sn bonds via dehydrogenative coupling 142
Dehydrogenative coupling catalyzed by transition-metal and f-block element complexes 143
Polystannanes 143
Tin Cages and Clusters 145
Lead 147
Introduction 147
Synthetic Methods 147
Reactivity of the Pb-Pb Bond 147
Structural Features of the Pb-Pb Bond 148
Diplumbanes 148
Synthesis 148
Oligoplumbanes 149
Lead Clusters 150
Conclusion 150
References 151
Chapter 1.04: Catenated Phosphorus Compounds 158
Introduction 158
Nomenclature 158
Neutral Compounds 166
Anionic Compounds 174
Cationic Compounds 181
Conclusion 185
References 185
Chapter 1.05: Catenated Compounds - Group 15 (As, Sb, Bi) 190
Introduction 190
Dipnicogen Compounds 191
Monocycles (RE)n (E=As, Sb, Bi) 197
Catena Tri- and Tetra-Pnicogen Compounds and Extended Chains (RE)x (E=As, Sb, Bi) 202
Heteromonocycles with Pnicogen-Pnicogen Bonds 202
Neutral Homoatomic Organometallic Pnicogen Polycycles (RnEm) (E=As, Sb, Bi; n 203
Heteroatomic Polycycles with Pnicogen-Pnicogen Bonds 205
Cationic Species with Pnicogen-Pnicogen Bonds 205
Extended Ribbons in Bismuth Subhalides 207
Anionic Catenated Species of As, Sb, and Bi 207
Ligand-Free Pnicogen Cluster Anions with Heteroatoms 211
Neutral Adducts with Dative Pnicogen-Pnicogen Bonds 212
Catena Species in Complexes and Clusters 212
Naked Neutral En Species (E=As, Sb, Bi) 213
Conclusion 214
References 214
Chapter 1.06: Catenated Sulfur Compounds 218
Background and Scope 218
Neutral Systems: The Allotropes of Sulfur 219
The Gas-Phase Allotropes - S2, S3, and S4 219
Forms of S8 and the Effects of Pressure upon This Allotrope 220
Forms at ambient pressure, and biologically produced S8 220
The effects of pressure upon S8 221
Polymerization of S8 222
The Smaller Rings - S6 and S7 222
The Larger Rings S9-S20: Preparation and Structure 222
Reactivity of S8 and the Larger Rings 224
Complexes of intact rings 224
Oxides of the cyclic allotropes 225
Homoatomic Cations of Sulfur 226
General Introduction 226
Preparation and Structure of Solid-State Sulfur Cations 226
The preparation and structure of salts of [S4]2 226
The preparation and structure of salts of [S8]2 226
The preparation and structure of salts of [S19]2 227
Bonding Within Sulfur Cations 227
Sulfur Cations in Solution 228
Sulfur Cations in the Gas Phase 229
Sulfur Cations within Zeolite Hosts 229
Polysulfide Anions 229
Free Polysulfide Anions 229
Polysulfides as Ligands 230
Conclusion 231
References 233
Chapter 1.07: Catenated Compounds - Group 16 (Se, Te) 236
Introduction 236
Elemental Selenium and Tellurium and Related Mixed Chalcogen Systems 238
Polymeric Selenium and Tellurium Allotropes 238
Selenium- and Tellurium-Containing Chalcogen Rings 239
General 239
Homocyclic selenium molecules 239
Homocyclic tellurium molecules 239
Selenium and tellurium rings in metal complexes 241
Heterocyclic chalcogen molecules 241
Selenium sulfides 241
Tellurium-containing chalcogen rings 243
Selenium- and Tellurium-Containing Ions 244
Polyatomic Selenium and Tellurium Cations 244
General 244
E42 245
E6n+ (n=2, 4) 245
E8n+ (n=2, 4) 246
En2+ (n>8) 248
Polyatomic Selenium-Halogen and Tellurium-Halogen Cations 248
General 248
Selenium-chlorine and selenium-bromine cations 249
Selenium-iodine and tellurium-iodine cations 249
Se2I42 249
E6I22+ (E=Se, Te) 249
Anions 251
General 251
Acyclic polyselenides and polytellurides 252
Cyclic polyselenides and polytellurides 252
Extended polytelluride networks 254
Catenated Main Group Polyselenides and -tellurides 255
Selenium and Tellurium Halogenides 255
Group 15 Polyselenides and -tellurides 258
Group 14 Polyselenides and -tellurides 262
Group 13 Polyselenides and -tellurides 265
Transition Metal Complexes 267
Conclusion 267
References 268
Chapter 1.08: Catenated Compounds - Group 17 - Polyhalides 272
Introduction 272
The Triiodide Ion 272
The Bonding in Trihalide Ions 274
Bonding Trends in Trihalides 275
Polyiodides 276
New Trends in Polyiodide Chemistry 279
Structural Confinement 279
Metal-Iodide/Iodine Compounds 280
Liquids and Solvent Effects 281
Polybromides - An Emerging Branch of Polyhalide Chemistry 281
Other Polyhalides 283
Applications 284
Optical Applications 284
X-Ray Contrast Agents 284
Triiodide Detection 284
Doping of Polymers and Carbons 284
Electrolytes 285
Conclusion 286
Acknowledgment 286
References 286
Chapter 1.109: Zintl Anions 290
Zintl Anions 290
What is a Zintl Anion? 290
History 290
Definitions and concepts 291
Synthetic routes 292
Discrete Polyanions in Zintl Phases of Group 14 and Group 15 and Their Dissolution Behavior 293
Homoatomic polyanions of group 14 in solid state 294
Clusters 294
E46- and rings 294
e9780080965291v2 1315
Front Cover 1315
Volume 2: Transition Elements, Lanthanides and Actinides 1318
Copyright 1319
Editorial Board 1320
Contributors 1322
Contents 1336
Preface 1350
Volume Editors' Introduction 1352
Crystal Structure and Chemical Bonding 1356
Chapter 2.01: Transition-Metal Perovskites 1356
Introduction 1356
Cooperative Octahedral Tilting Distortions in Perovskites 1357
Lone-Pair-Driven Instabilities in Perovskites 1359
Electronic Instabilities in Perovskites 1361
Polar Distortions in Perovskites Based on d0 B Cations 1361
Jahn-Teller Distortions and Orbital Ordering 1364
Charge Instabilities 1369
Instabilities Related to the Spin State and Magnetism 1371
Ordering Phenomena at Cation and Anion Sublattices of Perovskites 1371
B-Site Ordering 1371
Noncooperative Octahedral Tilting in 1:1 Ordered A2BBO6 Perovskites and A2BBF6 Elpasolites 1374
A-Site Ordering 1376
Ordering of Anion Vacancies in Perovskites 1377
Coupled Cation and Anion-Vacancy Ordering 1379
Aperiodic Order in Perovskites 1381
Mixed-Anion Perovskites: Oxynitrides and Oxyfluorides 1384
Conclusion 1387
Appendix 1388
Crystallographic Data on the 15 Tilt Systems in ABX3 Perovskites 1388
References 1389
Chapter 2.02: Chemistry of Polar Transition-Metal Oxides 1396
Introduction 1396
Polar Oxide Materials - Structure Types 1397
Perovskite and Perovskite-Related Materials 1397
BaTiO3 1398
KNbO3 1398
PbTiO3 1398
LiNbO3 and LiTaO3 1398
Aurivillius Phases 1399
m=1: (Bi2O2)(BO4) 1399
m=2: (Bi2O2)(AB2O7) 1400
m=3: (Bi2O2)(A2B3O10) 1400
m=4: (Bi2O2)(A3B4O13) 1401
m=5: (Bi2O2)(A4B5O16) 1401
Tetragonal Tungsten Bronzes 1401
Barium sodium niobate 1402
Strontium barium niobate 1402
Potassium lithium niobate 1402
Potassium sodium strontium barium niobate 1402
Lead barium niobate 1402
Multiferroic Materials 1403
Perovskites 1403
Hexagonal manganites 1403
Metal halide and oxy-halide systems 1403
Strategies on Designing Polar Oxide Materials 1403
Metal oxyfluoride systems 1405
Salt-Inclusion Solids 1406
Borates 1407
Functional Properties Associated with Polar Oxide Materials 1407
Second-Harmonic Generation 1409
Measurement of SHG and data interpretation 1409
Piezoelectricity 1410
Sample preparation and measurements 1410
Direct piezoelectric measurements 1410
Converse piezoelectric measurements 1411
Pyroelectricity 1411
Sample preparation and measurement 1412
Pyroelectric current 1412
Pyroelectric charge 1412
Ferroelectricity 1413
Sample preparation and hysteresis loop 1413
Conclusion 1414
Acknowledgment 1414
References 1414
Chapter 2.03: Ruddlesden-Popper Phases and Derivatives: Homologous Series of Transition Metal Oxides 1418
Introduction 1418
Intergrowth of Stoichiometric Perovskite Layers with Single RS Layers 1419
The n=1 Members 1419
The n=2 Members 1420
Other n Members 1420
Oxygen-Deficient RP Phases 1420
The n=1 Members 1420
The n=2 Members 1421
Intergrowth of Perovskite Layers with Multiple RS-Like Layers: The Thallium and Bismuth RP Derivatives 1423
Intergrowths Involving Double RS-Like Layers: [R. S.]2.[Pe]n Intergrowths 1424
Intergrowths Involving Triple RS Layers, [RS]3-[Pe]n 1426
The n=1 members 1426
The n=2 members 1430
The n=3 and n=4 members 1431
Intergrowths Involving Larger RS Layers 1432
Creation of Ordered Oxygen Vacancies in Perovskite and RS Layers: The Lead and Mercury RP Derivatives 1432
The Lead Cuprates 1433
Mercury Cuprates 1434
`Insertion´ of Additional Fluorite-Type Layers between Pyramidal Copper Layers in Cuprates 1438
Substitution of Carbonate Layers for RS Layers in RP-Type Phases: Copper Oxycarbonates 1440
Shearing Perpendicular to RP Layers: The Collapsed Layered Oxides 1443
The Sr4Fe6O13-Type Structure 1446
Tubular Oxides 1446
Conclusion 1454
References 1454
Chapter 2.04: Zintl Phases with d-Metal 1458
Introduction 1458
Zintl Phases - Definition 1458
d-Orbitals and Zintl Phases 1458
Synthesis 1459
Direct Reaction of the Elements 1459
Flux Reactions 1459
d0 Transition Metal Zintl Phases 1459
dx Transition Metal Zintl Phases 1461
Compounds of the ThCr2Si2 Structure Type 1461
Compounds of the Ca14AlSb11 Structure Type 1461
Other Structure Types 1462
Properties 1463
Conclusion 1464
References 1464
Chapter 2.05: Transition-Metal Pnictides 1466
Abbreviations 1466
Introduction 1466
Crystal Chemistry 1467
Pnictides with Isolated Pn3- Ions 1467
Binary compounds 1467
Equiatomic ternary compounds AMPn 1468
Metal-Rich Pnictides 1468
Binary compounds 1469
Ternary compounds 1473
Polypnictides with PnPn Bonds 1475
Binary polypnictides 1475
Ternary polypnictides with electropositive metals 1477
Pnictide Oxides 1482
Physical Properties 1483
Magnetism 1483
Pnictides as Thermoelectric Materials 1484
Iron-Pnictide Superconductors 1484
Conclusion 1487
References 1487
Chapter 2.06: Low-Valency Nitridometalates 1492
Introduction 1492
Preparative Aspects 1494
The Family of Nitridometalates (Systems A-AE-TM (Groups 5-10)-N) 1496
Low-Valency Nitridometalates (Systems Li-AE-TM (Groups 7-10)-N) 1498
Li2[LiN]-Type Structures and Ternary Variants with Substitution Scenarios [(Li,TM)N] and [(Li1-xTMx)N] 1499
Ternary and Quaternary Phases Without Substitution Effects 1504
Dumbbell anions (TM+1) 1505
Infinite-chain anions (TM+1) 1506
Infinite-chain anions (TM<+1) 1507
Layered anions (TM<+1) 1508
Chemical Bonding and Physical Properties 1510
The Role of Carbon during Nitridometalate Synthesis 1512
Conclusion 1512
Acknowledgment 1513
References 1513
Chapter 2.07: Fluorides and Oxide-Fluorides of d-Transition Elements 1516
Introduction 1517
Synthetic Routes 1517
Fluorides 1517
Oxide-Fluorides and Fluoride Salts 1517
Structural Characteristics 1518
Structures of MX2 and Derived Phases 1518
Rutile, diaspore, anatase, and derived phases 1519
Rutile-type MIIF2 1519
Dirutiles MIMIIIF4 1519
Distorted edge-sharing structures 1519
Diaspore-derived phases 1519
Fluorinated anatase 1519
Trirutile, A2MF6, AMMF6, and derived phases 1519
Trirutile phases 1519
Structural relationships between A2MF6 and AMMF6 1519
Structures of MX3 and AxMX3 Compounds 1520
MX3, MMX6, and derived phases 1520
MX3 phases 1520
MMX6 and derived phases 1520
Ordered cubic ReO3 type phases 1520
LiSbF6 type with cationic vacancies 1520
ReO3 type with cationic vacancies 1521
AMX3, A2MMX6: perovskites, elpasolites, and derived phases 1521
AxMX3, AMMX6, and related phases: pyrochlores and weberites 1521
Layered 2D Structures 1522
MnX3n+1 phases 1522
AMX4, A2MX4, Ruddlesden-Popper, and derived phases 1523
A2MX6 and Aurivillius phases 1523
Chiolite A5M3X14 1523
Fluoride pnictides 1523
1D Structures 1523
Simple chains 1524
Complex chains 1525
Noble-metal coordination complexes 1525
Miscellaneous 1526
The ternary system BaF2-CuF2-AlF3 1526
Complex structures of MXn polyhedra 1526
Fluoride Salts and Condensed Fluoro-Anions 1527
Fluoride borates and fluoride carbonates 1527
Fluoride borates 1527
Fluoride carbonates 1527
Fluoride silicates, fluoride phosphates, and fluoride sulfates 1527
Fluoride silicates 1527
Tavorite-type fluoride phosphates and fluoride sulfates 1527
Na2FePO4OH-type fluoride phosphates 1528
Chemical modifications 1528
Fluoride phosphates 1529
Fluorophosphates 1529
Fluoride sulfates 1529
Fluoride titanates or vanadates 1529
Physical-Chemical Properties 1530
Ferroelasticity, Ferroelectricity, and Multiferroism 1530
Ionic Mobility in Fluorides 1530
High-Tc Superconductivity 1532
Magnetism 1532
Optical Properties 1533
Acido-Basic Properties and Catalytic Activity 1535
Conclusion 1536
References 1536
Chapter 2.08: High-Valent Fluorides and Fluoro-Oxidizers 1542
Introduction 1544
Oxidation-State Concept 1544
Main-Group Elements 1545
Period I - H-He 1545
Period II - Li-Ne 1545
Lithium 1545
Beryllium 1545
Boron 1545
Carbon 1546
Nitrogen 1546
Oxygen 1546
Fluorine 1546
Neon 1546
Period III - Na-Ar 1547
Sodium 1547
Magnesium 1547
Aluminum 1547
Silicon 1547
Phosphor 1547
Sulfur 1547
Chlorine 1547
Argon 1548
Period IV - K-Kr 1548
Potassium 1548
Calcium 1548
Gallium 1548
Germanium 1548
Arsenic 1548
Selenium 1548
Bromine 1549
Krypton 1549
Period V - Rb-Xe 1549
Rubidium 1549
Strontium 1549
Indium 1549
Tin 1549
Antimony 1550
Tellurium 1550
Iodine 1550
Xenon 1550
Period VI - Cs-Rn 1550
Cesium 1550
Barium 1550
Thallium 1551
Lead 1551
Bismuth 1551
Polonium 1551
Astatine 1551
Radon 1551
Period VII - Fr-Ra 1551
Francium 1551
Radium 1551
Transition-Metal Elements 1552
The 3d Transition Metals 1552
Scandium 1552
Titanium 1552
Vanadium 1552
Chromium 1553
Manganese 1553
Iron 1554
Cobalt 1554
Nickel 1554
Copper 1554
Zinc 1554
The 4d Transition Metals 1555
Yttrium 1555
Zirconium 1555
Niobium 1555
Molybdenum 1555
Technetium 1555
Ruthenium 1555
Rhodium 1556
Palladium 1556
Silver 1556
Cadmium 1556
The 5d Transition Metals 1556
Lanthanum 1556
Hafnium 1557
Tantalum 1557
Tungsten 1557
Rhenium 1557
Osmium 1557
Iridium 1557
Platinum 1558
Gold 1558
Mercury 1558
The Lanthanide Series 1559
Cerium 1559
Praseodymium 1559
Neodymium 1559
Promethium 1559
Samarium 1559
Europium 1559
Gadolinium 1560
Terbium 1560
Dysprosium 1560
Holmium 1560
Erbium 1560
Thulium 1560
Ytterbium 1560
Lutetium 1560
The Actinide Series 1561
Thorium 1561
Protactinium 1561
Uranium 1561
Neptunium 1562
Plutonium 1562
Americium 1562
Curium 1562
Berkelium 1562
Californium 1562
Einsteinium 1563
Fermium 1563
Mendelevium 1563
Nobelium 1563
Lawrencium 1563
Strong Oxidizers 1563
General Trends and Summary 1565
Conclusion 1568
Acknowledgment 1568
References 1568
Relevant Website 1487
Chapter 2.09: Transition Metal Oxides Under Extreme Conditions 1578
Introduction 1578
High-Pressure Behavior of Me2O Oxides 1579
High-Pressure Behavior of TM Monoxides 1580
Interplay Between Structural, Magnetic, and Electronic States in MnO and Iron Group Metal Monoxides 1580
Cubic to rhombohedral structural and antiferromagnetic transitions in FeO and MnO 1580
High-pressure high-temperature behavior of MnO and iron group metal monoxides 1582
High-Pressure Behavior of Some Nonrock-Salt Structured Transition Metal Monoxides 1582
High-Pressure Behavior of TM Sesquioxides 1583
Structures of TM Sesquioxide Polymorphs 1583
Sc2O3 and Y2O3 1585
Ti2O3 1586
Cr2O3 1586
Mn2O3 1586
Fe2O3 1586
Rh2O3 and Effect of the d Electrons on Phase Transitions in TM Sesquioxides 1587
High-Pressure Behavior of TM Me3O4 Oxides 1587
Mn3O4 1587
Fe3O4 1588
High-Pressure Behavior of TM MeO2 Oxides 1588
Structures of Polymorphs of TM Dioxides 1589
TiO2, ZrO2, and HfO2 1590
CrO2 1591
RuO2, MnO2, IrO2, and OsO2 1592
Regularities in High-Pressure Behavior of TM Dioxides 1592
Conclusion 1592
Acknowledgment 1592
Relevant Websites 1593
References 1593
Chapter 2.10: Polyoxometalates: Synthesis and Structure - From Building Blocks to Emergent Materials 1596
Introduction 1596
History 1597
Classification 1597
Synthesis and Assembly 1600
Crystal Engineering by Cation Control 1600
Nonconventional and Chiral POMs 1601
Polyoxoniobates 1601
Uranium 1602
Palladium 1602
Peroxide Ligands 1602
Chirality 1603
Oxothiometalates 1604
Mo-Blue and Mo-Brown 1604
Analytical Tools 1605
Mass Spectrometry 1605
ESI-MS and CSI-MS 1605
IMS-MS 1607
Electrophoresis 1607
Surface Analysis 1608
POM-Organic Hybrids 1608
Frameworks 1609
POM-Based Frameworks 1610
Silver as the transition-metal linker 1610
Nonsilver-based frameworks 1611
Hybrid frameworks 1612
POM-MOFs 1613
Redox-Active POMs 1613
Devices, Catalysts, and Magnetism 1614
Catalysis 1614
Water splitting 1614
Catalysts 1615
Magnetism 1616
POM-Based Emergent Materials 1616
Nanostructures by Cation Exchange 1618
Tube growth at a solid-liquid interface 1618
Membrane growth at a liquid-liquid interface 1619
Soluble Colloids 1620
Hybrid-Based Nanostructures 1620
Formation of vesicles 1620
Surface studies 1620
Conclusion 1621
References 1622
From Clusters to Intermetallics 1626
Chapter 2.11: Clusters and Cluster Assemblies 1626
Introduction 1626
Main Structure Types 1628
Triangular Clusters 1628
Tetrahedral Clusters 1628
Octahedral Clusters 1628
Group 3 Elements 1629
Group 4 Elements 1631
Titanium 1631
Zirconium and Hafnium 1632
Group 5 Elements 1634
Vanadium 1634
Niobium and Tantalum 1635
Halide clusters 1635
Trinuclear and tetranuclear clusters 1635
Octahedral clusters 1637
Chalcogenide clusters 1640
Oxide clusters 1641
Nitride clusters 1642
Group 6 Elements 1643
Halides 1643
Trinuclear, tetranuclear, and pentanuclear clusters 1643
Octahedral and prismatic clusters 1644
Chalcogenides 1645
Triangular clusters 1645
Triangular clusters with the cluster core M3Q4 1645
Triangular clusters with the cluster core M3Q7 1645
Other examples of triangular chalcogenide clusters 1646
Tetrahedral clusters 1646
Octahedral clusters 1646
Chevrel phases 1646
Condensed clusters: M>6 1647
Extended solids 1648
Oxides 1648
Phosphides and Arsenides 1650
Group 7 Elements 1650
Halides 1650
Chalcogenides and Chalcohalides 1651
Triangular clusters 1651
Tetranuclear clusters 1651
Octahedral clusters 1651
Molecular complexes 1651
Extended solids 1652
Chemistry of the inner ligands 1654
Heterometal clusters 1654
Re9 and Re12 clusters 1654
Condensed clusters and extended M-M chains 1654
Phosphides and Arsenides 1655
Late Transition Metals 1655
Cuboidal Fe4S4 Clusters 1655
Prismatic Fe6S6 Clusters 1656
Octanuclear Clusters 1656
High-Nuclearity Clusters 1656
Nitrosyl Iron Clusters 1657
Conclusion 1658
References 1658
Chapter 2.12: Metal-Rich Compounds of the d-Metals 1666
General Introduction 1666
Fundamentals of the d-Metals 1667
Atomic Characteristics 1667
Solid-State Characteristics 1668
Similarities Between Late d-Metals and p-Elements 1672
What Defines `Metal-Rich´ for the d-Metals? 1673
Molecular Cluster Compounds 1673
Reduced d-Metal Halides and Chalcogenides 1673
Trinuclear clusters 1673
Tetrahedral clusters 1674
Octahedral clusters 1674
Nanosized Homo- and Heterometallic Pd(0)-Based Clusters 1675
Macromolecular Chalcogenide Clusters of the Coinage Metals 1676
Extended Cluster Compounds 1679
Condensed Octahedral Cluster Compounds 1679
Rare-Earth Elements as d-Metals 1681
Condensed Gold Clusters 1683
Binary Interstitial Compounds 1685
Nitrides 1685
Carbides 1686
Oxides 1686
Intermetallic and Metal-Metalloid Compounds 1686
d-p Compounds 1690
TX compounds 1690
T2X, TTX, and T3X compounds 1692
Heusler and half-Heusler compounds 1694
Magnetically ordered metal-rich borides 1695
Early-metal chalcogenides and pnictides 1696
T5X3 and T5X4 compounds 1697
Hume-Rothery Electron Compounds 1698
d-d Intermetallic Compounds 1701
Simple stoichiometries 1702
Topologically close-packed compounds 1704
Rare-earth/late d-metal-rich cases 1705
Ternary Interstitial Compounds 1706
Conclusion 1707
Acknowledgment 1708
References 1708
Chapter 2.13: Crystal Structure and Bonding in Intermetallic Compounds 1714
Introduction 1714
Definition 1714
Crystallographic Description 1714
Formation of Structure Patterns 1715
Bonding 1721
Conclusion 1726
Acknowledgment 1727
References 1727
Hybrid Materials 1730
Chapter 2.14: Nanostructured Inorganic-Organic Hybrid Semiconductor Materials 1730
Background and Introduction 1731
Binary Semiconductor Compounds of Group VI Elements 1731
Semiconductor Quantum Dots and Quantum Size Confinement 1733
Crystalline Inorganic-Organic Hybrid Semiconductor Materials 1734
Nanostructured Crystals and Structure-Induced QCE 1734
II-VI-Based Inorganic-Organic Hybrid Semiconductor Nanostructures 1735
Design, Synthesis, and Crystal Growth 1735
Crystal Structures 1736
The one-dimensional chain 1D-MQ(L) structures 1738
The two-dimensional single-layered 2D-MQ(L) structures 1738
The three-dimensional single-layered 3D-MQ(L)0.5 structures 1738
The 3D single-layered structures containing acyclic diamines 1738
The 3D single-layered structures containing cyclic diamines 1741
The two-dimensional double-layered 2D-M2Q2(L) structures 1741
Selected Properties 1742
Optical absorption and bandgaps 1742
The band structures 1746
Thermal stability 1748
Phase transitions 1751
Thermal expansion 1752
Photoluminescence and white-light emission 1755
Mechanical properties 1756
Thermal conductivity 1757
Magnetic properties 1757
Other properties 1757
III-VI-Based Inorganic-Organic Hybrid Semiconductor Nanostructures 1759
Other Types of Metal Group-VI-Based Hybrid Semiconductor Nanostructures 1762
Conclusion 1765
Acknowledgment 1766
References 1766
Modern Synthesis 1772
Chapter 2.15: Soft Chemistry Synthesis of Oxides 1772
Introduction 1772
Synthesis from Precursors 1773
Co-Precipitation Precursor Routes 1773
Sol-Gel Precursor Routes 1774
Inorganic polymer sol-gel precursors 1774
Alkoxide hydrolysis 1774
Metal chelate gels 1774
Organic polymer sol-gel precursors 1774
Synthesis in Solvents and Fluxes 1775
Solvothermal Synthesis 1775
Early transition-metal oxides 1775
Complex manganese oxides 1776
Flux Synthesis 1777
Low-Temperature Topochemical Synthesis 1777
Cation-Insertion Reactions 1778
Intercalation into framework oxide phases 1778
ReO3-type hosts 1778
MO2 rutile-type hosts 1779
AB2O4 spinel-type hosts 1780
Intercalation into layered binary oxide phases 1781
α-MoO3 1781
V2O5 1782
Intercalation into layered perovskite structures 1782
Dion-Jacobson phases 1782
Cation-deficient Ruddlesden-Popper Phases 1783
Aurivillius phases 1784
Cation Deintercalation Reactions 1784
α-NaFeO2-type phases 1784
LiCoO2 1784
NaCoO2 1785
Physical properties of A1-xCoO2 1786
AxNiO2 1787
LiVO2 1787
Lithium manganese oxides 1787
Titanates 1788
TiO2(R) 1788
TiO2(H) 1789
Anion Deintercalation Reactions 1789
`Cubic´ perovskite phases 1789
Ruddlesden-Popper phases 1792
Reductive fusion of perovskite sheets 1794
Structural selectivity 1794
Anion-Insertion Reactions 1795
Anion-deficient perovskites 1795
Structural stabilization 1796
Cation-ordered phases 1796
Ruddlesden-Popper phases 1797
Oxygen-insertion reactions 1797
Fluorination reactions 1798
Chlorine-insertion reactions 1799
Iodine-insertion reactions 1799
Redox-Neutral Topochemical Reactions 1800
Cation-substitution reactions 1800
NaFeO2-type phases 1800
Layered binary and ternary oxides 1801
Dion-Jacobson phases 1801
Ruddlesden-Popper phases 1802
Deintercalation 1803
Dehydration reactions 1803
Layer extraction 1804
Redox-neutral intercalation 1804
Salt intercalation reactions 1804
Intercalation of organic bases 1805
Conclusion 1805
References 1805
Chapter 2.16: Alkoxides and Alkoxosynthesis 1810
Nomenclature 1466
Introduction 1810
Synthetic Approaches to Metal Alkoxides 1811
Interaction of Metals with Alcohols 1811
Anodic Oxidation of Metals 1811
Alcoholysis of Metal Hydrides, Metal Alkyls, and Metal Alkylamides 1812
Metathesis of Metal Halides 1813
Alkoxylation of Metal Salts 1813
Alcohol Interchange Reactions 1813
Self-Assembly Synthesis of Heteroleptic and Heterometallic Alkoxides 1814
Molecular and Crystal Structures of Metal Alkoxides 1814
Mononuclear Alkoxides 1814
Dinuclear Alkoxides 1815
Trinuclear Alkoxides 1816
Tetranuclear Alkoxides 1816
Oligonuclear Structures 1817
Chemical Reactivity of Metal Alkoxides 1817
Ligand Exchange 1818
Hydrolysis and Condensation: Silicon Versus Metal Alkoxides 1820
Non-Hydrolytic Cleavage in Solution (Bradley Reaction; Guerbet Reaction) 1821
Thermolysis in the Gas Phase 1822
Thermolysis in a Melt and in Solid Phase: Metal-Organic Decomposition Versus Reaction Under Autogenic Pressure at Elevated ... 1822
Metal Alkoxides as Homogeneous Catalysts 1822
Metal Alkoxide Complexes as Molecular Magnets 1823
Conclusion 1824
References 1824
Chapter 2.17: Exothermic Metathesis Reactions 1826
Introduction 1826
Materials Synthesis 1828
Metal Borides and Aluminides 1828
Metal borides 1828
Metal aluminides 1829
Metal Carbides and Silicides 1829
Metal carbides 1829
Metal silicides 1832
Metal Nitrides 1833
Metal Phosphides, Arsenides, and Antimonides 1836
Metal phosphides 1836
Metal arsenides and antimonides 1837
Metal Oxides 1838
Metal Sulfides, Selenides, and Tellurides 1840
New Directions in Metathesis Reactions 1841
Solution-mediated metathesis 1841
Carbon nanotubes 1841
Nanocrystals 1842
Molecular precursor approaches 1842
Complex materials 1843
Conclusion 1843
References 1843
Chapter 2.18: New Chemistry of Noble Metals 1846
Introduction and Scope 1846
Oxidation States 1846
Relativistic Effects 1846
High Oxidation States 1847
Low Oxidation States 1848
Metal-Metal Bonds 1849
Generalities 1849
Examples 1850
Selected Compounds 1852
The Unique Xenono Gold Complexes 1852
Polyoxometalates 1853
Compounds with Oxoanions 1853
Selenates and selenites 1853
Sulfates 1854
Sulfate derivatives 1856
Nitrates, perchlorates, and iodates 1857
Phosphates and silicates 1859
Halides 1860
Chlorides 1860
Conclusion 1862
References 1862
Chemistry of f-elements 1866
Chapter 2.19: Volatile Compounds of Lanthanides 1866
Introduction 1866
Halides 1867
Complexes with Amides 1868
Alkoxides and Siloxides 1869
Borohydrides 1872
Organolanthanide Complexes 1872
Phthalocyanines 1874
beta-Diketonates 1874
Synthesis 1876
Tris-Diketonates [Ln(dik)3] 1877
Mixed-Ligand Lanthanide beta-Diketonates [Ln(dik)3(Q)n] 1879
Lanthanide Tetrakis-beta-Diketonates 1883
Lanthanide beta-Ketoiminates 1884
Lanthanide Dialkyldithiocarbamates 1884
Carboxylates 1885
Conclusion 1886
References 1886
Chapter 2.20: Low-Valence Compounds of the Lanthanoids 1890
Introduction 1890
Hydrogen in Lanthanoid Metals 1891
Valence Instability and Intermediate Valence 1892
Mixed Valence in Lanthanoid Halides 1893
Mono- and Dihalides of Lanthanoids 1896
Discrete and Condensed Clusters 1899
Discrete Clusters 1900
Chain Structures 1904
Layer Structures 1907
Three-Dimensional Frameworks 1911
Compounds with Boron and Carbon 1912
Lanthanoids and Carbon 1914
Lanthanoids and Boron 1917
Boride Carbides of Lanthanoids 1921
Disorder Phenomena 1923
Partial Order in Cluster Phases 1924
Variation of Cluster Sizes 1926
Disorder on Multiple Scales 1927
Structure Property Relations 1929
d Electrons Acting on the 4f Core Electrons 1929
f Electrons Acting on the System of d Electrons 1930
p-d Mixing in Compounds of Rare-Earth Metals 1932
References 1933
Chapter 2.21: Complex Ternary Transition-Metal Hydrides and Hydridometalates 1938
Introduction 1938
Experimental 1938
Synthesis 1938
Characterization 1939
Alkali and Alkaline-Earth Metal Hydridometalates 1940
Alkali-Metal-Transition-Metal Hydrides and Hydridometalates 1940
Alkaline-Earth Transition-Metal Hydrides and Hydridometalates 1946
Rare-Earth Metal Transition-Metal Hydrides and Hydridometalates 1951
Conclusion 1952
Acknowledgment 1952
References 1952
Chapter 2.22: Transuranium Inorganic Chemistry 1956
Introduction 1956
Importance of Oxidation States 1957
Aqueous Chemistry 1957
Hydrolysis 1959
Carbonate Complexation 1959
Binary Compounds 1960
Halides: Neptunium 1960
Halides: Plutonium 1960
Americium 1961
Curium, Berkelium, and Californium 1961
Oxides 1961
Solid State Chemistry of Np 1961
Compounds of Np(V) and Np(VI) 1962
Conclusion 1964
References 1964
Chapter 2.23: Crystal Chemistry of Uranium Oxides and Minerals 1966
Introduction 1966
U(III) Oxocompounds 1967
U(IV) Oxocompounds 1967
U(V) Oxocompounds 1968
U(VI) Oxocompounds 1970
Coordination Geometries 1970
Crystal Chemistry of U(VI) Oxides and Hydroxides: Anion-Topology Approach 1970
Variable Population of Anion Topologies: From Oxides and Hydroxides to Oxocompounds 1972
Stereoisomerism in Anion Topologies 1972
Modular Design of Anion Topologies 1973
Linkage Mode of Layers Contributes to Structural Diversity 1974
Polytypism in U(VI) Oxocompounds 1975
Anion Topologies with U-Populated Hexagons: Uranyl Polyborates 1976
Complex Uranium Oxides with Octahedrally Coordinated High-Valent Cations (Mo, W) 1976
Open Topologies in Uranyl Oxocompounds with Tetrahedral Oxoanions 1977
Graph theory analysis of structure topologies 1977
Topological diversity of uranyl oxosalts with tetrahedral oxoanions with monodentate coordination 1978
Distinguishing between topological isomers 1978
The concept of basic graph and derivative topologies 1979
Orientational stereoisomerism and the origin of chirality 1979
Basic graphs and modular design of structure topologies 1980
Low-dimensional structures 1980
Topological diversity of uranyl oxosalts with tetrahedral oxoanions with bidentate coordination 1980
Monodentate and bidentate coordination of uranyl ions by tetrahedral oxoanions: statistical analysis of observed 1982
Monodentate coordination 1982
Bidentate coordination 1982
Open structures with mu-O2-, mu-OH-, or mu-F- bridges between uranyl ions 1983
Microporous Framework Structures 1984
General construction principles 1984
Combinatorial polymorphism in uranium(VI) framework structures: the case of uranyl polyphosphates 1984
Uranium(VI) Oxocompounds with Nanoscale Structure 1986
Uranyl peroxide nanospheres 1986
Uranyl selenate nanotubules 1986
Dimensional Reduction in Uranium(VI) Oxocompounds 1989
CCIs in Uranium(VI) Compounds 1990
Conclusion 1991
References 1991
Chapter 2.24: Lanthanides and Actinides in Ionic Liquids 1996
Introduction 1996
Overview of Ionic Liquids 1997
Solvation and Complex Formation in Ionic Liquids 1999
Complexes of Functionalized Ionic Liquids 2003
Ionic Liquids with f-Element-Containing Anions 2004
Crystal Chemistry of Complexes Crystallized from Ionic Liquids 2005
Electrochemistry 2006
Electrodeposition of Metals and Alloys 2008
Solvent Extraction 2009
Applications of Ionic Liquids in the Nuclear Fuel Cycle 2011
Soft Luminescent Materials 2014
Synthesis of Lanthanide-Containing Nanoparticles in Ionic Liquids 2016
Lanthanide-Mediated Organic Reactions in Ionic Liquids 2017
Conclusion 2024
References 2025
e9780080965291v3 2029
Front Cover 2029
Volume 3: Bioinorganic Fundamentals and Applications: Metals in Natural Living Systems and Metals in Toxicology and Medicine 2032
Copyright 2033
Editorial Board 2034
Contributors 2036
Contents 2050
Preface 2064
Volume Editors' Introduction 2066
Bioinorganic Fundamentals and Applications: Metals in Natural Living Systems and Metals in Toxicology and Medicine 2054
Chapter 3.01: Fe Acquisition 2068
Introduction 2068
Siderophore-Mediated Iron Uptake 2068
Structural Features of Siderophores 2069
Iron-binding functionalities 2069
Catechol 2069
Hydroxamic acid 2071
α-Hydroxycarboxylic acid 2072
Mixed-ligand functionalities 2073
Amphiphilic siderophores 2073
Siderophore Thermodynamics 2074
Chirality of Fe(III)-Siderophore complexes 2074
Transport of Fe(III)-Siderophore Complexes 2074
Gram-negative bacteria 2074
Gram-positive bacteria 2078
Variations of the mechanism of Fe(III)-siderophore transport 2078
Microbial Production of Multiple Siderophores 2079
Iron Release from Ferric Siderophore Complexes 2080
Heme-Mediated Iron Uptake 2081
Transferrin and Lactoferrin-Mediated Iron Uptake 2082
Ferrous Iron Transport 2083
Regulation of Bacterial Iron Transport 2084
Fur Protein 2084
Conclusion 2084
Acknowledgment 2085
References 2085
Chapter 3.02: Fe Transport and Storage Related to Humans and Pathogens and Oxygen 2088
Introduction 2088
When and Why Living Cells Need Iron 2088
An Introduction to Ferritins 2088
Iron Transport 2089
Intestinal Iron Absorption 2090
Iron Absorption by Cells Inside the Body: Tf, TfR, and Endocytosis 2090
Iron Biominerals and the Protein Nanocages - Structure/Function in the Ferritin Family 2091
Eukaryotic Ferritins 2091
Iron entry and mineralization 2091
Iron exit and mineral dissolution 2092
Catalysis and mineral growth 2092
Microbial Ferritins 2093
Occurrence and general features 2093
Structure 2094
The Ftn maxi-ferritin, 24mer cage 2094
BFR maxi-ferritin, 24mer cage 2094
Dps mini-ferritins, 12-mer cage 2094
Catalysis 2094
The catalytic centers. The catalytic sites in microbial ferrtins vary much more in structure and mechanism than eukaryotic ... 2095
Ftn 2095
The BFR catalytic center 2095
The Dps catalytic center 2095
Mechanisms of mineralization 2096
Fe/O Artillery in Disease: Ferritin in Host/Pathogen Relationships 2096
When Ferritin Synthesis and Breakdown Change 2097
How Ferritin Synthesis and Breakdown Change 2097
Ferritin protein synthesis 2097
Ferritin protein degradation 2098
Conclusion 2099
References 2099
Chapter 3.03: Metal-Regulated Gene Expression 2102
General Considerations 2102
Introduction 2102
Elements Involved in Metal-Regulated Gene Expression 2102
Structural Families Involved in Prokaryotic Metal-Regulated Gene Expression 2103
Allosteric Linkage in Metal-Regulated Gene Expression 2103
Metal-Dependent Gene Regulation in Prokaryotes 2106
Coordination Geometry as a Primary Determinant for Metal Selectivity 2106
Signal Propagation in Bacterial Systems 2109
Metal-Dependent Gene Regulation in Eukaryotes 2110
Introduction 2110
Iron Regulation in Eukaryotes 2110
Zinc Regulation in Eukaryotes 2111
Copper Regulation in Eukaryotes 2113
The Role of the DNA 2113
Conclusion 2114
References 2114
Chapter 3.04: Toxicology (Pb, Hg, Cd, As, Al, Cr, and Others) 2118
Introduction: Toxicity Versus Essentiality 2118
Toxic Elements (Abundance, Origin, and Targets) 2119
Quintessentially Toxic Elements 2120
Lead 2120
Mercury 2121
Cadmium 2123
Arsenic 2124
Aluminum 2126
Chromium 2126
Others 2127
Nickel 2127
Tin 2127
Selenium 2128
Detoxification and Detoxication 2128
Conclusion 2129
References 2129
Relevant Websites 2130
Chapter 3.05: Recent History of Heme-Containing Proteins: Advances in Structure, Functions, and Reaction Intermediate Det ... 2132
Introduction/Heme Characteristics 2133
Spectroscopic Methods for Heme Proteins 2134
Globin Heme-Containing Proteins 2136
Hemoglobin 2136
Myoglobin 2138
Iron Uptake and Storage Heme Proteins 2140
HasA Hemophores 2140
Bacterioferritin 2141
Small Molecule Sensors 2143
FixL 2143
CooA 2145
Soluble Guanylate Cyclase 2147
Cytochromes 2149
Cytochrome b5 2149
Cytochrome c 2150
Small Molecule Enzymes 2152
Cytochrome c Oxidase 2152
Catalase 2154
Peroxidases 2155
Horseradish Peroxidase 2155
Dehaloperoxidase 2157
Chloroperoxidase 2159
Monooxygenases 2161
Cytochrome P450 2161
Nitric Oxide Synthase 2163
Conclusion 2165
References 2166
Chapter 3.06: Iron-Sulfur Centers: New Roles for Ancient Metal Sites 2170
Type of Centers and Variability of Coordination 2170
Basic Structures and Cluster Coordination Modes 2170
[1Fe] cluster 2171
[2Fe-2S] cluster 2171
Rieske proteins 2172
[3Fe-4S] cluster 2172
Aconitase 2174
[4Fe-4S] cluster 2174
Complex Iron-Sulfur Clusters 2175
Unique clusters 2176
Fuscoredoxin 2176
Sulfite reductase 2177
Nitrogenase (FeMo-co and P-cluster) 2178
Organometallic and mixed-metal clusters 2178
Hydrogenases 2178
[FeFe] hydrogenases 2179
[NiFe] hydrogenases 2180
Carbon monoxide dehydrogenases/acetyl-CoA synthases 2181
Redox and spectroscopic properties of the C-cluster 2181
Redox and spectroscopic properties of the A-cluster 2182
Iron-Sulfur Proteins Involved in New Functions 2182
Biosynthesis of Iron-Sulfur Clusters 2182
ISC system 2183
SUF system 2184
CIA system 2185
Biosynthesis of complex iron-sulfur clusters 2185
Generation of the nonprotein ligands 2186
Scaffolds supporting the cluster assembly 2186
Cluster inclusion into the enzyme 2187
Direct Catalysis at Iron-Sulfur Clusters 2187
Radical-SAM enzymes 2188
Examples from each class of radical-SAM enzymes 2190
Lysine 2,3-aminomutase 2190
Biotin synthase 2190
Pyruvate formate-lyase activating enzyme 2190
New atypical SAM-dependent enzymes 2191
Iron-sulfur (de)hydratases 2192
Aconitase 2193
IspG and IspH involved in prokaryotic isoprenoid biosynthesis 2194
ADP-ribosyltransferase enzymes (unusual Fe-S cluster) 2197
Other enzymatic activities 2197
Iron-Sulfur Clusters Involved in Metabolic Regulation 2198
Post-transcriptional regulation of iron homeostasis 2198
Transcription regulators 2199
Rrf2 family 2199
RirA, rhizobial iron regulator A 2199
NsrR, nitrite-sensitive transcription repressor 2200
IscR, Iron-sulfur cluster biogenesis regulator 2201
CRP family 2202
Fumarate and nitrate reductase 2202
Anaerobic regulation of arginine deiminase and nitrate reduction 2202
Other transcription regulators 2203
Sensing reactive oxygen species - SoxR 2203
WhiB family of transcription regulators 2204
Nitrogen regulation (NreB) 2204
The Role of Iron-Sulfur Clusters in DNA-Processing Enzymes 2205
DNA repair glycosylases 2205
Conclusion 2206
Acknowledgment 2207
References 2207
Chapter 3.07: Copper Enzymes 2216
Introduction 2216
Scope of the Chapter 2216
Copper Chemistry Basics 2217
O2 Utilization 2219
Fundamental Properties of Dioxygen 2219
Hemocyanin 2219
Tyrosinase 2220
Other Monooxygenases 2223
Noncoupled dinuclear monooxygenases 2223
Particulate methane monooxygenases 2225
Cellulose monooxygenase 2226
Dioxygenases (Quercetin 2,3-Dioxygenase) 2227
Copper Oxidases 2228
Mononuclear copper oxidases 2228
Copper amine oxidase 2228
Galactose oxidase 2229
Multicopper oxidases 2232
Heme-copper oxidases 2233
Cytochrome oxidase 2233
Models 2235
Superoxide Dismutase 2237
NOX Processing 2238
Nitrite Reductase 2238
Nitrous Oxide Reductase 2240
Conclusion 2241
Acknowledgment 2242
References 2242
Chapter 3.08: Zinc in Biology 2246
Introduction 2246
Zinc Transporters, Trafficking, and Sequestration 2247
ZnTs and ZIPs 2247
Metallothioneins 2249
Vesicles 2250
Albumin 2250
Bacterial Zn(II) Transport Systems 2250
ABC transporters 2251
P-type ATPases 2251
Cation diffusion facilitators 2251
Zinc Enzymes 2251
Carbonic Anhydrases 2252
Advances in protein and model studies of α-CAs 2252
Protein design 2253
Model studies 2254
beta-, gamma-, delta-, and zeta-CAs 2256
Inhibition of CAs 2257
CO2 sequestration using CAs and bioinspired CA-type constructs 2258
Mononuclear Zinc Hydrolases 2258
Matrix metalloproteinases 2258
Histone deacetylases 2260
Angiotensin-converting enzyme 2262
Dinuclear (Co-Catalytic) Zinc Hydrolases 2262
Metallo-beta-lactamases 2262
Glutamate carboxypeptidase II 2264
Active Site Dynamic Zinc Coordination Chemistry 2265
Alcohol Dehydrogenases 2265
Cobalamin-Dependent (MetH) and -Independent (MetE) Methionine Synthases 2266
Conclusion 2268
References 2268
Chapter 3.09: Bioinorganic Neurochemistry 2274
Introduction 2275
Brain Anatomy - A Brief Overview 2276
Metals in Neurotransmission and Memory 2278
Sodium and Potassium Distribution 2278
Action potential 2278
Na+/K+ adenosine triphosphatase 2279
Ion Channels in Neurotransmission 2279
Voltage-gated ion channels 2279
Specialized K+ channels 2280
Calcium 2281
Calcium homeostasis 2281
Calcium-binding proteins 2283
Calcium: neurotransmission and memory 2283
Transition-Metal Distribution and Function 2283
Iron 2284
Iron uptake in glial cells 2285
Iron uptake in neurons 2285
Iron storage and release 2285
What are the molecular details of iron trafficking in the brain? 2286
Iron proteins in the brain 2286
Copper 2287
Cellular copper import via Ctr1 2287
Copper chaperones 2288
Storage and excretion of copper 2288
Cu metalloenzymes in the brain 2288
Zinc 2289
Zinc import and export in brain cells 2289
MT and zinc storage 2290
Zn-metalloproteins in the brain 2290
Synaptic zinc 2292
Other Metals (Mn, Ni, and Al) 2292
Manganese 2292
Nickel and aluminum 2293
Diseases 2293
Epilepsy 2293
Voltage-gated Na+, K+, and Ca2+ channels 2293
Oxidative stress and iron in epileptogenesis 2294
Zinc and epileptogenesis 2294
Other Diseases Associated with Na/K/Ca Channels 2294
Chronic pain 2294
Inherited migraine 2294
Bipolar disorder 2294
Ischemia 2294
Ischemic cerebral edema 2295
Spreading depolarization 2295
A role for Zn2+ in ischemia 2295
Oxidative stress and metals during ischemic events 2295
Ataxia 2295
Friedreich's ataxia 2295
Multiple Sclerosis 2296
Protein Aggregation Disorders 2296
Alzheimer's Disease 2296
Parkinson's Disease 2299
Huntington's Disease 2299
Creutzfeldt-Jakob Disease 2300
Amyotrophic Lateral Sclerosis 2300
Bioinorganic Interventions 2301
Molecular Imaging 2302
Fluorescence (optical) imaging 2302
Magnetic resonance imaging 2302
Microprobe x-ray fluorescence imaging 2302
Mass spectrometry: secondary ion mass spectrometry and LA-ICP-MS 2302
Metal-Based Therapies 2303
Conclusion 2303
References 2303
Chapter 3.10: Nitric Oxide Signaling 2308
Introduction to Nitric Oxide Signaling 2308
Nitric Oxide Synthase 2309
NOS Electron Transport 2311
NOS Monooxygenase Reaction I 2312
NOS Monooxygenase Reaction II 2314
Soluble Guanylate Cyclase 2315
Interactions of NO with Heme Iron 2316
Ligand Discrimination in sGC 2318
Structure and Function in the sGC Heme Domain 2319
The Mechanism of Activation of sGC by Nitric Oxide 2322
The role of excess NO 2323
NO binding at the heme proximal site 2323
NO binding at nonheme sites 2323
Structural changes involved in NO activation of sGC 2324
Protein S-Nitrosation 2325
S-Nitrosation via NO Autooxidation to N2O3 2325
S-Nitrosation via Thiyl Radical Recombination with NO 2326
Transition Metal-Catalyzed S-Nitrosation 2326
Conclusion 2326
References 2326
Chapter 3.11: Molybdenum Enzymes 2330
Introduction and Scope 2331
The Molybdenum Cofactor 2331
SO Family of Pyranopterin Molybdenum Enzymes 2332
Background 2332
Active Site Coordination Environment 2334
Spectroscopic Studies 2335
EPR spectroscopy 2335
Electronic absorption and MCD spectroscopies 2336
Raman spectroscopy 2337
Reaction Coordinate of SO and Nitrate Reductase 2338
Xanthine Oxidase 2339
Background 2339
Active Site Coordination Environment 2341
Xanthine oxidoreductases 2341
Carbon monoxide dehydrogenases 2342
Spectroscopy 2343
Spectroscopic studies on XOR and AO 2343
Spectroscopic studies on CODH 2344
Computational Probes of the Reaction Coordinate in XO Family Enzymes 2344
The reaction coordinate of XOR and AO 2344
The reaction coordinate of molybdenum-dependent CODH 2346
DMSO Reductase 2346
Background 2346
Active Site Coordination Environment 2347
Type I enzymes 2347
Prokaryotic periplasmic nitrate reductases 2347
Formate dehydrogenases 2347
Type II enzymes 2347
Prokaryotic Nar 2347
Ethylbenzene dehydrogenase 2348
Type III enzymes: DMSO reductase and TMAO reductase 2348
Arsenite oxidase 2348
Spectroscopic Probes of Ground- and Excited-State Electronic Structures 2349
DMSO reductase 2349
Prokaryotic Nap 2350
Prokaryotic assimilatory nitrate reductases 2350
Formate dehydrogenases 2351
Detailed Investigations of Enzyme Reaction Coordinates 2351
Reaction coordinate of DMSO reductase 2351
Reaction coordinate of prokaryotic respiratory Nap and Fdh 2352
Nitrate reductase 2352
Formate dehydrogenase 2352
Ethylbenzene dehydrogenase 2352
Nitrogenase 2353
Nitrogen 2353
Reaction Overview 2353
Structure of Molybdenum-Containing Nitrogenase 2353
Fe protein 2353
MoFe protein 2354
Reaction Mechanism 2354
Lowe-Thorneley kinetic scheme 2354
Distal and alternating reaction pathways 2354
Studies of isolated intermediates of nitrogenase 2355
Conclusion 2356
Note Added in Proof 2356
Acknowledgment 2356
References 2357
Relevant Website 2360
Chapter 3.12: Nickel Bioinorganic Systems 2362
Nickel Coordination Chemistry 2362
Coordination Geometries 2362
Redox Chemistry 2363
Environmental Chemistry of Nickel 2364
Nickel Essentiality and Toxicity in Animals 2364
Nickel Essentiality and Toxicity in Plants 2366
Microbial Nickel Biochemistry 2367
Nickel Trafficking 2367
Nickel uptake 2367
Outer membrane transport 2367
NiCoT permeases 2367
NikABCDE - ABC transporter 2369
Nickel homeostasis 2369
NikR as an example of regulation of nickel uptake 2369
RcnR as an example of regulation of nickel export 2371
KmTr/NmtR: Mycobacteruim tuberculosis Ni2+/Co2+ transcription factors 2371
Nickel storage - Hpn of H. pylori 2371
Nickel exporters 2371
Nickel Enzymes 2372
Enzymes with nonredox nickel centers 2372
Urease 2372
Glyoxylase 2374
Acireductone dioxygenase 2375
Nickel redox enzymes 2375
Hydrogenase 2375
Nickel-dependent superoxide dismutase 2379
Carbon monoxide dehydrogenase 2380
Acetyl coenzyme A synthase 2382
Methyl coenzyme M reductase 2382
Conclusion 2384
References 2384
Relevant Website 2389
Chapter 3.13: Vanadium Biochemistry 2390
Introduction 2391
Vanadium Chemistry 2391
Enzymes Containing Vanadium 2392
Nature's Halogenation Catalysts: VHPOs 2392
The peroxidase reaction and general description of the haloperoxidase enzymes 2392
Vanadium bromoperoxidase 2392
Vanadium chloroperoxidase 2393
Comparing the haloperoxidases 2394
Substrate activity by haloperoxidases 2394
Phosphatase activity by haloperoxidases 2396
Nitrogenases 2397
General overview 2397
Structural perception and amino acid sequence 2397
Enzyme catalysis 2398
Dinitrogen reduction 2398
Carbon monoxide reduction 2399
Vanabins 2399
Organisms Accumulating Vanadium 2399
Tunicates 2399
General overview 2399
Oxidation state of vanadium in tunicates 2400
Tunichromes 2401
Vanadium accumulation and reduction in tunicates 2401
Amavadine 2402
General overview 2402
Structure and reactivity 2402
Fan Worm 2404
Insulin Enhancing Effect of Vanadium Compounds 2404
Conclusion 2405
Acknowledgment 2405
References 2405
Chapter 3.14: Hydrogenases 2410
Biological Relevance of Hydrogenases 2410
Genetic and Structural Classification of Hydrogenases 2412
Structural Features of [NiFe]-Hydrogenases 2412
[NiFeSe]-hydrogenases 2414
Biosynthesis of [NiFe]-Hydrogenases 2414
Structural Features of [FeFe]-Hydrogenases 2415
Biosynthesis of [FeFe]-Hydrogenases 2416
[Fe]-Hydrogenase Structure 2416
Biosynthesis of [Fe]-Hydrogenases 2417
Reactivity of Hydrogenases 2418
The Coordination Chemistry of H2 2418
Redox States of Hydrogenases 2420
Redox states of [NiFe]-hydrogenases 2420
Redox states of [FeFe]-hydrogenases 2422
Catalytic Mechanism of Hydrogenases 2423
The catalytic mechanism of [NiFe]-hydrogenases 2424
The catalytic mechanism of [FeFe]-hydrogenases 2425
The catalytic mechanism of [Fe]-hydrogenases 2426
Potential Biotechnological Relevance of Hydrogenases 2428
Technological Relevance of Hydrogenases 2428
Medical Relevance of Hydrogenases 2430
Synthetic Models of Hydrogenases 2430
[NiFe]-Hydrogenase Models 2431
Functional models of [NiFe] hydrogenases 2433
Synthetic Models of [FeFe]-Hydrogenases 2434
Structural models of [FeFe]-hydrogenases 2434
Functional models of [FeFe]-hydrogenases 2436
Synthetic Models of [Fe]-Hydrogenases 2441
Brief Overview of Experimental and Theoretical Methods Used to Study the Chemical Properties of Hydrogenases 2442
X-Ray Crystallography 2442
Fourier Transform Infrared Spectroscopy 2442
X-Ray Absorption Spectroscopy 2443
Mössbauer Spectroscopy 2443
EPR Spectroscopy 2443
Methods to Evaluate the Catalytic Activity of Hydrogenases 2443
DFT Calculations 2445
Conclusion 2445
References 2445
Chapter 3.15: Complex Systems: Photosynthesis 2452
Introduction 2452
Photosynthesis: The Inspiration for an Artificial Leaf 2453
The Light and Dark Reactions in Photosynthesis 2454
Metals in Photosynthesis 2455
Manganese 2455
Calcium 2456
Copper 2457
Iron 2457
Nickel 2457
Photosystem II 2458
Overview 2458
Light Harvesting and Charge Separation 2458
RC Cofactors and Electron Transfer 2459
Electron transfer in PSII 2459
Redox-active D1-Y161 or YZ 2459
The OEC 2460
Nonheme Fe between QA and QB 2460
Cytochrome b559 2461
Cytochrome c550 2461
Water Oxidation by the OEC: Structure and Mechanism 2462
X-ray crystallographic studies and the OEC 2462
Continuous wave and pulsed EPR studies 2462
XAS of the OEC 2466
Substrate water exchange in the OEC 2468
FTIR studies 2469
The Ca(II) ion in the OEC 2470
Proton egress from the OEC 2471
Chloride in PSII 2472
O―O bond formation 2473
Mechanism for water oxidation in the OEC 2474
Model complexes for the OEC 2474
Other Metal Centers in Photosynthesis 2474
Blue Copper Site in Plastocyanin 2474
Iron-Sulfur Centers 2479
Rieske center in cytochrome b6f complex 2479
Fe4S4 centers in PSI 2480
Fe2S2 ferredoxin as an electron mediator between PSI and FNR 2481
Hydrogenases 2481
Ribulose-1,5-Bisphosphate Carboxylase-Oxygenase 2483
Artificial Photosynthesis 2484
Conclusion 2485
References 2485
Chapter 3.16: B12 Enzymes, Function, and Small Molecules as Models 2490
Introduction 2490
B12 Absorption, Cellular Uptake, and Enzymatic Processes 2492
B12 Models 2492
Overview of Model Types 2494
Cobaloximes, the Prototypical Cobalamin Model 2494
Cobaloximes with Different Equatorial Moieties 2497
Properties and Structure of Cobalamins 2498
Structure and Comparison to Simple Models 2501
Axial Dissociation Equilibria and Relationships with Structure 2501
B12 Bioconjugates for Medical Applications 2502
B12 Transport Proteins 2503
B12 Binding to Transport Proteins in Mammals 2503
B12 Transport in Bacteria 2505
Decyanation of Vitamin B12 2506
Adenosyltransferase 2506
Methyltransferase Enzymes 2507
MeCbl MetH 2508
Corrinoid-Dependent Methyltransferase in Archaea and Bacteria 2510
Anaerobic Dehalogenases 2511
Adenosylcobalamin-Dependent Enzymes 2512
Isomerases 2513
Eliminases 2515
Ribonucleotide Reductase 2516
Conclusion 2517
Acknowledgment 2518
References 2518
Chapter 3.17: Small Molecule Models: Cu, Ni, Co 2522
Introduction 2522
Activation of O2: Modeling Oxygenase and Oxidase Intermediates 2524
Copper-Oxygen Intermediates 2524
Dicopper complexes 2524
Monocopper complexes 2527
Multicopper complexes 2529
Nickel-Oxygen Intermediates 2530
Cobalt-Oxygen Intermediates 2532
N2O and NO: Modeling the Reduction of NOx Species in Biology 2533
Copper-NO and -NO2- Complexes 2534
Modeling Nitrous Oxide Reductase 2535
Activation of CO and CO2: Modeling Reduction and Hydration 2536
CO2 Reduction and CO Oxidation 2536
Modeling Acetyl-CoA Synthase 2538
Hydration of CO2: Modeling Carbonic Anhydrase 2539
Modeling Hydrolase Intermediates: H2O Activation 2540
Hydrolysis of Phosphate and Carboxylic Esters 2540
Copper complexes 2541
Nickel and cobalt complexes 2541
Nitrile Hydratase Models 2543
Nickel complexes 2544
Cobalt complexes 2544
Urease Models 2546
Nickel complexes 2546
Cobalt complexes 2547
Conclusion 2547
Note added in proof 2548
Activation of O2: Modeling Oxygenases and Oxidases 2548
N2O and NO: Modeling the Reduction of NOx Species 2548
Activation of CO and CO2 2549
Modeling Hydrolase Intermediates: H2O Activation 2549
References 2549
Chapter 3.18: Small Molecule Models for Nonporphyrinic Iron and Manganese Oxygenases 2554
Introduction 2554
Structural Diversity at Nonheme Iron- and Manganese-Dependent Oxygenases 2555
Synthetic Modeling of Nonheme Iron- and Manganese-Dependent Oxygenases 2555
Basic Structures in the Modeling of Nonheme Iron Enzymes 2556
Carboxylate-Containing Systems 2557
Modeling the 2His-1-Carboxylate Facial Triad with Bulky Carboxylates 2557
Enzymes Models 2559
Rieske Oxygenases 2559
Acetylacetone Dioxygenase (DKe1) 2563
α-KG-Dependent Oxygenases 2566
α-KG-dependent halogenases 2568
Phenylpyruvate dioxygenase 2570
Aliphatic C―C cleaving enzymes related to α-KG-dependent oxygenases 2572
Cysteine Dioxygenase 2574
Lipoxygenases 2578
Structural modeling of FeIII, MnIII hydroxide(alkoxide) species 2579
C―H cleavage by the FeIII and MnIII hydroxide(alkoxide) species 2582
Formation of high-spin alkylperoxide-ferric complexes 2583
Ring-Cleaving Oxygenases 2583
Catechol dioxygenases 2584
Intradiol-cleaving catechol dioxygenases 2584
Extradiol-cleaving catechol dioxygenases 2586
Basis for understanding regioselectivity in catechol dioxygenases 2591
3-Hydroxyanthranilate 3,4-dioxygenase 2592
Flavonol dioxygenases 2592
Oxidizing Species in Nonheme Iron Synthetic Models with Relevance to Iron Oxygenases 2594
Fe-(su)peroxo 2594
Biological relevance 2594
Synthetic models 2594
Iron-superoxo 2594
Iron-(hydro)peroxo 2595
Iron-alkylperoxo 2598
Fe-oxo 2601
Biological relevance 2601
Synthetic models 2602
Iron(III)-oxo 2602
Iron(IV)-oxo with S=1 2603
Iron(IV)-oxo with S=2 2609
Iron(V)-oxo 2611
Oxidizing Species in Manganese Synthetic Models with Relevance to Oxygenases 2611
Mn-(su)peroxo, Hydroperoxo, and Alkylperoxo 2611
Mn-superoxo 2611
Mn-peroxo 2612
Mn-hydroperoxo and Mn-alkylperoxo 2616
Mn-oxo and Mn-(oxo/hydroxo) 2617
Mn-oxo 2617
Mn-bis(oxo/hydroxo) 2618
Reactivity of Mn-hydroxo and Mn-oxo 2620
Conclusion 2625
References 2625
Chapter 3.19: Metalloprotein Design 2632
Introduction 2632
Metalloprotein Design in De Novo Designed Scaffold 2632
Metal-Induced Self-Assembly of Random Coils 2633
De Novo Design of Proteins That Bind Heme or Iron-Sulfur Clusters 2633
Helix-Loop-Helix Motifs as Models for Artificial Diiron Proteins and Metallonucleases 2634
De Novo Metalloprotein Design in Parallel Three-Stranded Coiled Coils 2635
De Novo Designed Beta Sheets 2636
Metalloprotein Design in Native Scaffolds 2636
Design of Heme Proteins in Native Scaffolds 2636
Design of myoglobin variants with peroxidase and p450 activity 2637
Engineering oxidase activity into Mb 2637
Redesign of Mb into a functional NOR 2638
Redesign of peroxidases with new manganese peroxidase-like activity 2639
Redesign of Copper Proteins 2639
Design of Nonheme Iron-Containing Proteins in Native Scaffolds 2643
Design of Zn Proteins in Native Scaffolds 2645
Design of Metalloproteins Containing Metals Other Than Cu, Fe, and Zn 2646
Metalloprotein Design Incorporating Unnatural Amino Acids 2647
Metalloprotein Design Containing Non-Native Cofactors 2650
Selection of Protein Scaffolds and Non-Native Cofactors 2650
Noncovalent Approach 2650
Dative anchoring in combination with secondary stabilization interactions 2650
Supramolecular assembly 2651
Covalent Approach 2651
Combinatorial Selections and Hybrid Methods in Metalloprotein Design 2652
Conclusion 2656
References 2657
Chapter 3.20: Spectroscopic Methods for Understanding Metals in Proteins 2662
Introduction 2662
Ground-State Methods 2663
Cu(II) Complexes: S=1/2 2663
High-Spin Fe(III): S=5/2 2665
High-Spin Fe(II): S=2 2665
Ligand Field Excited States 2667
CT Excited States 2670
Resonance Raman Spectroscopy 2672
x-Ray Spectroscopy 2675
Closed-Shell Cu(I) Sites 2675
The Ground-State Wavefunction 2676
Metal K-edge 2676
Metal L-edges 2677
Ligand K-edges 2678
Recent Advances in Synchrotron-Based Spectroscopic Methods 2679
L-Edge XAS and RIXS 2679
L-edge XAS, DOC 2679
1s2p RIXS 2681
Nuclear Resonance Vibrational Spectroscopy 2683
Conclusion 2687
Acknowledgment 2688
References 2688
Chapter 3.21: Metal-Ion Interactions with Nucleic Acids and Their Constituents 2690
Introduction 2692
General Considerations 2692
Relevant Metal Ions and Some of Their Properties 2692
Potential Coordinating Atoms on RNA 2693
Some acid-base considerations on potential binding sites 2693
Some comments on micro acidity constants, intrinsic basicities, and tautomeric equilibria 2694
Acid-base properties of some less common natural and also artificial nucleosides 2695
Metal-Ion Affinities of the Phosphodiester Bridge as well as of Mono-, Di-, and Triphosphates 2697
Metal-Ion Interactions with Sugar-Hydroxyl Groups 2698
Metal-Ion Affinities of Nucleobases 2699
Metal-Ion Binding to Neutral Nucleobase Residues 2699
Metal-Ion Binding to Anionic Purine Residues 2700
Metal-Ion Binding to Negatively Charged Pyrimidine Residues 2701
Metal-Ion Binding to Nucleotides 2701
General Considerations on Chelate Formation 2701
Nucleoside Monophosphate Complexes 2703
Stabilities and structures of complexes formed with natural nucleoside 5'-monophosphates 2703
Complexes of some analogs and rare or artificial nucleoside monophosphates 2704
Complexes of nucleoside 2'- and 3'-monophosphates 2705
Complexes of Nucleoside 5'-Di- and 5'-Triphosphates 2706
Metal-Ion-Binding Properties of Dinucleotides 2708
The Phosphodiester Bridge and the Guanine Residue May Affect Complex Stability of a Dinucleotide 2708
A Thiophosphate Bridge in a Dinucleotide May Lead to Discrimination in Metal-Ion Binding 2709
Metal-Ion Affinities of Individual Sites of Single-Stranded Nucleic Acids 2710
Metal-Ion Binding to RNAs 2710
Solvation Content of Metal Ions 2711
Thermodynamics of Metal-Ion Binding to RNA 2712
Indirect methods 2712
Hydrolytic cleavage experiments 2712
Oxidative cleavage experiments 2713
Spectroscopic methods 2713
Metal-Ion Binding Motifs in RNA 2714
Tandem GC base pairs 2714
GU wobble pairs 2715
Sheared GA base pair 2715
Loop E motif or metal-ion zipper 2716
Mg2+ Clamp 2716
AA platform 2716
Nucleobase tetrads 2716
Further motifs 2717
Binding of Kinetically Inert Metal Ions 2718
Binding of Pt2+ to RNA 2718
Binding of other inert metal ions 2718
Metal-Ion Binding in the Helix Center 2718
Binding of Metal-Ion Complexes 2719
Hexammine complexes with Co3+ and other metal ions 2719
Further complexes 2720
Metal Ions and Their Role in Folding and Dynamics of RNA 2720
Metal Ions and Their Role in RNA Catalysis 2720
General Effects of Metal Ions on the Observed Catalytic Rate 2720
Two-Metal-Ion Mechanism 2721
Electrostatic Influence of Metal Ions 2721
Conclusion 2722
Acknowledgment 2722
References 2722
Relevant Websites 2727
Medicinal and Toxicology 2728
Chapter 3.22: Protein-Binding Metal Complexes: Noncovalent and Coordinative Interactions 2728
Introduction: Coordination Interactions Between Metal Complexes and Proteins 2728
Carbonic Anhydrase Inhibitors 2729
Phosphatase and Kinase Inhibitors 2731
Vanadium Complexes 2731
Other Transition-Metal Ion Complexes 2732
Protease Inhibitors 2733
Cysteine Proteases 2733
Aspartic Proteases (Human Immunodeficiency Virus Type-1 Protease) 2733
Matrix Metalloproteinases 2734
Serine Proteases 2735
Other Enzyme Inhibitors 2735
Chemokine Receptor Antagonists 2736
Coordination Interactions with Peptides 2737
Coordination Interactions with Proteins (Other) 2737
Lysozyme, Transferrin, and Ferritin 2737
Serum Proteins 2738
Zinc Finger Proteins 2740
DOTA, Ethylenediaminetetraacetic Acid, and DTPA Metal Complex Binding to Proteins 2741
Binding to Histidine and Aspartate Tagged Proteins 2743
Protein Crosslinking: Proteins as Ligands 2744
Other Applications 2745
Medical Imaging 2745
Catalysis 2746
Prion Binding, Presenter Protein, and Antitumor Compounds 2746
Conclusion 2747
References 2747
Chapter 3.23: Hydroxamic Acids: An Important Class of Metalloenzyme Inhibitors 2750
Introduction 2751
Chemistry of Hydroxamic Acids 2751
Acid-Base Chemistry 2751
Metal-Binding Ability 2753
Hydroxamic Acids as Enzyme Inhibitors 2754
Hydroxamic Acids as Matrix Metalloprotease Inhibitors 2755
Hydroxamic Acids as Carbonic Anhydrase Inhibitors 2758
Hydroxamic Acids as Histone Deacetylase Inhibitors 2760
Hydroxamic Acids as Urease Inhibitors 2763
Hydroxamic Acids as Leukotriene A4 Hydrolase Inhibitors 2765
Hydroxamic Acids as Prostaglandin-H-Synthase (COX) Inhibitors 2766
Hydroxamic Acids as 5-Lipooxygenase Inhibitors 2768
Hydroxamic Acids as Peptide Deformylase Inhibitors 2771
Conclusion 2773
Acknowledgment 2773
References 2774
Chapter 3.24: Noncovalent DNA Binding of Metal Complexes 2776
Introduction 2777
DNA Structure 2778
Modes of Metal Complex Binding 2779
Electrostatic Binding 2780
e9780080965291v4 3081
Front Cover 3081
Volume 4: Solid-State Materials, Including Ceramics and Minerals 3084
Copyright 3085
Editorial Board 3086
Contributors 3088
Contents 3102
Preface 3116
Volume Editors' Introduction 3118
Solid State Materials - General 3120
Chapter 4.01: Synthetic Methodologies 3120
Introduction to Solid-State Synthesis: Synthesis versus Preparation 3120
Methods of Preparation of Equilibrium Phases 3121
Direct Reaction of the Elements 3121
Gas-Solid Reactions 3121
Ceramic Methods 3121
Methods Involving Fine Dispersions of Starting Materials 3123
Coprecipitation Methods 3124
Sol-Gel Methods 3125
Microwave Techniques 3125
Reactions in Media 3126
Hydrothermal and solventothermal methods 3126
Flux methods 3126
Metathesis and Assisted Metathesis 3128
The Growth of Crystals 3129
From the melt-congruent systems 3129
Vapor-transport methods 3130
Methods of Preparation of Nonequilibrium Phases 3130
Quenching 3130
Topochemical Methods 3131
Atom-by-Atom Deposition Techniques 3132
Conclusion 3133
References 3133
Chapter 4.02: Materials from Extreme Conditions 3136
Introduction 3136
Electronic Structure Changes in Elements and Compounds: Implications of High-Pressure Chemistry 3137
Metals, Alloys, and Superconductors 3137
Hydrogen 3139
Unusual Bonding Changes at High Pressure 3139
Thermodynamic Considerations 3140
High-Density Phases Formed by the First-Row `Light´ Elements 3140
Introduction 3140
Diamond, c-BN, and High-Density Carbon Polymorphs 3140
Compressing C60/C60 Fullerenes, Graphite, and C-Based Layered Solids 3141
Icosahedral Borides 3141
High-Density C3N4 and Related Carbon Nitride Materials 3144
CO2 and CO 3145
N2, O2 solid polymorphs and N-O-C compounds 3146
Tetrahedrally Bonded Orthonitrates, Orthocarbonates, and High-Density Borate Compounds 3147
High-P Solid-State Chemistry of Oxide Minerals and Related Materials 3148
Introduction 3148
High-Pressure SiO2 Polymorphs 3148
Silicate and Germanate Spinels, Ilmenite and Garnet Phases 3150
Silicate Perovskites and Post-Perovskite Structures 3150
Perovskite-Structured and Related Oxide Materials 3151
Nitride Spinels and Related Compounds 3152
Nitrides, Pnictides, and Chalcogenides: Also Intermetallic Compounds, Zintl Phases, and Semiconductor Clathrates 3153
Introduction 3153
High-Pressure Nitrides, Carbides, and Pnictides 3153
Intermetallic Compounds, Zintl Phases, and Semiconductor Clathrates 3154
Planetary Ices, Inorganic Frameworks, and Amorphous Solids 3155
Liquid H2O and H-Bonded Ice Structures 3155
Zeolites, MOFs, and Polyoxometallates 3155
Liquids, Glasses, and Amorphous Solids 3156
Conclusion 3157
Acknowledgment 3157
References 3157
Chapter 4.03: Oxides: Their Properties and Uses 3166
Introduction 3166
Perovskites 3166
Aurivillius Phase 3171
Ruddlesden-Popper Structures 3175
Brownmillerites 3177
Pyrochlores 3181
Spinels 3186
Delafossites 3187
Conclusion 3188
References 3188
Chapter 4.04: Compound Luminescent Semiconductors: Their Properties and Uses 3192
History of Phosphors 3192
Different Phosphors 3192
Bandgap Transition Phosphors 3193
Intra-Atomic Transition Phosphors 3193
Luminescence from Nano-Phosphors 3195
Luminescence from Persistence Phosphors 3196
Energy Transfer in Multiple Doped Phosphors 3197
Up- and Down-Conversion Phosphors 3198
Other Phosphors 3200
Phosphor Applications 3202
Cathode Ray Tubes 3202
Flat Panel Displays 3203
Field emission displays 3203
Plasma display panels 3203
Fluorescent Lamps 3203
x-Ray Screens and Scintillators 3203
Conclusion 3203
Acknowledgment 3204
References 3204
Chapter 4.05: Photoluminescent Zeolite-Type Lanthanide Silicates 3206
Zeolites and Related Materials 3206
Introduction 3206
Mixed Heteropolyhedra Framework Silicates 3207
Synthesis 3207
Properties and Applications 3208
Catalysis 3208
Separation over membranes 3208
Cation exchange 3208
Magnetic properties 3208
Optical properties 3208
Photovoltaic properties 3209
Drug (NO) delivery 3209
Photoluminescent Microporous Lanthanide Silicates 3209
Intra-4f Luminescence 3209
Engineering Optical Centers in Materials: Grand Challenges 3211
Structure and Optical Properties of Lanthanide Silicates 3211
Visible-light emission 3211
Montregianite-related materials 3211
Sazhinite-related materials 3212
Tobermorite-related materials 3213
Other materials 3215
Infrared-light emission 3217
X-ray scintillation 3217
Materials with unusual light-emitting features 3218
Materials for bimodal imaging of biological systems 3224
Conclusion 3226
Acknowledgment 3227
References 3228
Chapter 4.06: Nonclassical Crystals: Crystallographically Ordered Nanocrystal Superstructures 3230
Introduction 3230
Mesocrystals 3230
Mesocrystals Formed by Organic Matrix-Mediated Nanocrystal Alignment 3231
Mesocrystals Fromed by Physical Field-Induced Nanocrystal Alignment 3233
Mesocrystals Formed by Mineral Bridge-Mediated Nanocrystal Assembly 3235
Mesocrystals Formed by Space Constraint-Confined Nanocrystal Assembly 3236
Mesocrystals Formed by Oriented Attachment-Induced Nanocrystal Assembly 3238
Mesocrystals Formed by Nanocrystal Alignment in the Presence of Additives with Multiple Roles 3239
Single Crystals with Dislocations 3240
Imperfect Oriented Attachment 3240
Screw Dislocation-Driven Growth of Single Crystals 3241
Mesoporous Films with Oriented Nanocrystalline Walls 3241
Conclusion 3243
Acknowledgment 3243
References 3244
Chapter 4.07: Negative Thermal Expansion (Thermomiotic) Materials 3246
Introduction to Thermal Expansion 3248
Why Are Negative Thermal Expansion (Thermomiotic) Materials Interesting? 3248
Thermal Expansion and Mechanical Properties of Materials 3248
Mechanisms of NTE 3249
Lattice Vibrations 3249
Rigid-Unit Modes 3250
Macroscopic NTE 3250
Other NTE Mechanisms 3250
NTE and Its Relationship to Other Physical Properties 3251
Heat Capacity and Related Properties 3251
Thermal Conductivity 3252
Mode Grüneisen Parameter 3252
Phonon Dispersion Relations and Density of States 3252
Phase Transitions 3252
Applications of Thermomiotic Materials 3253
Current and Potential Applications 3253
Criteria for Applications 3253
Properties of the CTE tensor 3253
Chemical and thermodynamic criteria 3254
Mechanical criteria 3254
Synthesis and Characterization Tools 3254
Synthesis 3254
Solid-state synthesis at high temperature 3254
Soft-chemistry approaches 3255
Sol-gel synthesis 3255
Co-precipitation 3256
Hydrothermal synthesis 3256
Laser synthesis 3256
Microstructure 3257
Sintering, porosity, and microcracking 3257
Effects of particle morphology 3257
Coatings, surface treatments, and binders 3257
Experimental Determination of Thermal Expansion 3257
Diffraction techniques 3257
Dilatometry 3258
Discrepancies between diffraction and dilatometric results 3258
Raman Spectroscopy 3259
Inelastic Neutron Scattering 3259
X-Ray Absorption Spectroscopies 3259
Computational Methods 3260
Types of Thermomiotic Materials 3260
Metal Oxides and Related Structures 3260
AM2O8 3260
AM2O7 3261
A2M3O12 3261
A2M4O15 3261
AMO5 3262
AO3 and related structures 3262
Lithium aluminum silicates 3262
M2O 3262
Zeolites and aluminophosphates 3262
Perovskites and antiperovskites 3263
Metal Cyanides 3263
M(CN)2 3263
Ax[M(CN)6] (x=1, 1.5, 3) 3263
MCN 3264
Clathrates 3264
MOF Materials 3264
NaSICON 3265
Nanomaterials 3265
Other Structures 3265
Composites and Solid Solutions 3265
Composite materials 3265
Solid solutions 3266
Conclusion 3266
References 3266
Relevant Websites 3270
Solid State Materials and Electronics 3272
Chapter 4.08: The Electronic Structure and Properties of Solids 3272
Introduction 3272
Oxides: Excellent Insulators, Excellent Metals, and the World's Best Superconductors 3273
Non-Interacting or Non-Correlated Electrons: Energy Band Model of Metals, Insulators, and Semiconductors 3275
Interacting or Correlated Electrons: The Mott-Hubbard Model of Metals, Insulators, and Semiconductors 3277
Elementary Mechanisms and Models for the MIT 3280
The Mott MIT 3281
Disorder-Induced Electron Localization: The Anderson MIT 3282
Variable Range Hopping in Disordered Systems Below the MIT 3283
Short Mean-Free Paths and Localization: The Mott-Ioffe-Regel Criterion 3284
The Goldhammer-Herzfeld Dielectric Catastrophe 3286
Superconductivity 3288
Background 3288
High-Temperature Superconductivity in Cuprates 3290
Conclusion 3293
Acknowledgment 3294
References 3294
Chapter 4.9: Compound Semiconductors: Chalcogenides 3296
Introduction 3296
Cadmium Chalcogenides 3298
Cadmium Sulfide 3298
CdS nanoparticles 3299
CdS thin films 3300
Chemical bath deposition 3301
Cadmium Selenide 3301
CdSe nanoparticles 3302
CdSe thin films 3303
Chemical bath deposition 3304
Cadmium Telluride 3304
CdTe thin films and nanoparticles 3305
Zinc Chalcogenides 3305
Zinc Sulfide 3305
Zinc sulfide nanoparticles 3306
Zinc sulfide thin films 3307
Chemical bath deposition 3308
Thin-film deposition at liquid-liquid interface 3309
Zinc Selenide 3309
Zinc Telluride 3310
Zinc Oxide 3311
ZnO NCs 3311
Zinc oxide thin films 3312
Mercury Chalcogenides 3314
Mercury Sulfide 3314
Mercury Selenide 3316
HgSe nanoparticles 3316
HgSe thin films 3318
Mercury Telluride 3318
HgTe nanoparticles 3319
HgTe thin films 3320
Ternary II-Chalcogenide Materials 3320
Cadmium Zinc Sulfide 3321
Cadmium Zinc Telluride 3321
Cadmium Mercury Sulfide 3321
Cadmium Mercury Selenide 3322
Cadmium Mercury Telluride 3323
Mercury Zinc Sulfide 3324
Mercury Zinc Selenide 3324
Conclusion 3325
Relevant Websites 3325
References 3325
Chapter 4.10: Metals — Gas-Phase Deposition and Applications 3330
Introduction 3331
Gas-Phase Deposition Techniques 3331
Chemical Vapor Deposition 3332
Atomic Layer Deposition 3332
Metal Deposition 3332
Main-Group Metals 3332
Group 2 3332
Beryllium 3332
Magnesium 3333
Group 13 3333
Aluminum 3333
Indium 3336
Group 14 3336
Silicon 3336
Germanium 3337
Tin 3338
Lead 3339
Group 15 3340
Arsenic 3340
Antimony 3340
Bismuth 3340
Transition Metals 3340
Group 4 3340
Group 5 3341
Vanadium 3341
Niobium 3342
Tantalum 3342
Group 6 3342
Chromium 3342
Molybdenum 3344
Tungsten 3345
Group 7 3347
Manganese 3347
Rhenium 3348
Group 8 3348
Iron 3348
Ruthenium 3350
Osmium 3353
Group 9 3355
Cobalt 3355
Rhodium 3359
Iridium 3359
Group 10 3360
Nickel 3360
Palladium 3364
Platinum 3366
Group 11 3368
Copper 3368
Copper(I) complexes 3370
Copper(II) complexes 3372
Silver 3375
Gold 3378
Gold(I) complexes 3379
Gold(III) complexes 3380
Group 12 3381
Zinc 3381
Cadmium 3382
Mercury 3382
Conclusion 3382
Acknowledgment 3382
References 3382
Chapter 4.11: Magnetic Solid-State Materials 3390
Introduction 3391
Magnetocaloric Materials 3392
Concepts 3392
Classes of Magnetocaloric Materials 3393
Alloys 3393
RCo2 compounds 3393
Gd-Ge-Si-based compounds 3393
MnAs-based compounds 3394
Fe2P-based compounds 3394
La-Fe-Si-based compounds 3394
Ni-Mn-Ga-based compounds 3395
Manganites 3395
Composites 3397
Metallic glasses 3397
Outlook 3397
ME Materials 3398
ME Coupling in Solids 3398
Material Classes 3399
`Proper´ ME materials 3399
`Improper´ ME materials 3400
Chiral magnets 3400
Geometric ferroelectrics 3400
Exchange striction magnets 3401
Charge-ordered compounds 3401
Topological insulators 3402
Composites 3402
Outlook 3403
Dilute Magnetic Semiconductors 3403
Concepts 3404
II-VI-Based DMS 3404
III-V-Based DMS 3405
Oxide-Based DMS 3405
Zinc oxide-based DMS 3406
SnO2-based DMS 3406
TiO2-based DMS 3406
Defect-Mediated Magnetism in DMS 3406
Outlook 3407
Permanent Magnets 3407
Concepts 3408
Rare-Earth Magnets 3408
Exchange-Spring Magnets 3409
Outlook 3413
Magnetic Materials for Biomedical Applications 3413
Magnetic Hyperthermia 3413
Concepts and requirement 3413
Ferrites and other oxides 3414
Metallic nanoparticles 3416
Medical Imaging 3416
Drug Delivery 3417
Outlook 3417
Magnetic Materials for Microwave Applications 3418
Essentials of Microwave Magnetic Materials 3418
Spinel Ferrites 3418
Hexaferrites 3419
Garnets 3420
ME Composites 3421
Carbon Nanotube Magnetic Composites 3421
Outlook 3421
Spintronic Materials 3421
Heusler Alloys 3422
Electronic and magnetic properties 3423
Origin of gap and Slater-Pauling behavior 3423
Other Alloys 3424
Oxides 3425
Outlook 3426
Giant Magneto-Impedance Materials 3426
Concepts 3426
GMI in Alloys 3427
GMI in Oxides 3428
Outlook 3428
Conclusion 3428
References 3430
Chapter 4.12: One-Dimensional Inorganic Nanomaterials for Energy Storage and Production 3436
Introduction 3436
Synthesis of 1D Nanomaterials 3436
Crystal Growth from Solution: The Solvothermal Approach 3437
Template-assisted growth of 1D nanomaterials 3437
Nanowires from the Gas Phase: Chemical Vapor Deposition 3438
Electrospinning 3442
Lithium Ion Batteries 3445
Cathode Materials 3446
Anode Materials 3448
Generation of Hydrogen from Solar Energy 3452
Conclusion 3457
Acknowledgment 3458
References 3458
Chapter 4.13: Defining and Using Very Small Crystals 3462
Introduction 3462
Size and Shape Effects on NCs 3463
Surface Chemistry When Making and Using Inorganic NCs 3465
Synthesis of NCs 3467
NCs of Semiconductors 3467
NCs of Metals 3470
Synthesis of Au and Ag NCs 3471
Citrate and other aqueous phase reduction methods 3471
Two-phase reduction 3471
Synthesis of Iron Oxide NCs 3472
Arrested precipitation 3472
Thermal decomposition 3472
Tuning the Ligand Shell 3472
Ordered Assemblies of NCs 3473
One- and Low-Dimensional Arrangements 3473
2D Arrays 3473
3D Superlattices 3474
Colloidal Crystals 3475
Applications of Inorganic NCs 3476
Environment 3476
Magnetic sorbents for uptake of ionic contaminants 3477
Photocatalytic degradation of organic pollutants 3477
Light-Energy Conversion 3478
Biomedical Applications 3480
Bio-labeling using inorganic NCs 3480
Plasmonic NCs for bioanalysis 3481
Applications of iron oxides to biological systems 3482
Conclusion 3482
References 3483
Molecular Materials 3490
Chapter 4.14: Molecular Magnets 3490
Introduction 3490
Scope 3490
History 3490
A Very Brief Introduction to Magnetochemistry 3491
Techniques 3492
Slow Relaxation of Magnetization 3492
Magnetic hysteresis and thermal activation 3492
The origin of slow magnetization relaxation in SMMs 3493
Quantum tunneling of magnetization 3494
Magnetocaloric Effect 3494
Chemical Considerations 3495
Single-Molecule Magnets 3495
SMMs of Manganese 3495
The family of [Mn12O12(O2CR)16L4] cages 3496
Hexametallic manganese oximes 3499
A {Mn84} SMM 3500
Exchange biasing of SMM behavior 3500
One-dimensional, two-dimensional, and three-dimensional arrays of Mn4 cages 3500
SMMs Involving Iron(III) Ions 3501
SMMs Involving Further 3d-Metal Ions 3502
Heterometallic SMMs 3504
4f-Based SMMs 3506
SMMs on Surfaces 3507
High-Spin Cages with Low Anisotropy as Magnetic Coolants 3508
QIP Using Molecular Nanomagnets 3508
Conclusion 3510
References 3510
Naturally Occurring Materials 3516
Chapter 4.15: Perovskite Defect Chemistry as Exemplified by Strontium Titanate 3516
Nonstoichiometry and Doping 3516
The Impact of Defect Chemistry on Structure 3517
The Ideal Perovskite Structure 3517
Accommodation of Cation Substitutions 3517
Accommodation of Deficiency 3518
Accommodation of Oxygen Excess 3520
The Effect of Defect Chemistry on Properties 3520
Sintering and Microstructure 3520
Unit Cell Size 3520
The Extent of Reduction 3521
Meaning and importance of the extent of reduction 3521
Reduction in titanates 3522
Electronic Conductivity 3526
Electronic conduction in the perovskite lattice 3526
Factors that decide the conductivity of titanates 3526
B-Site Cation Segregation from A-Site-Deficient Perovskites 3529
Reasons behind the phenomenon 3529
Different manifestations of the B-site segregation 3530
Driving the formation of nanoparticles from perovskite frameworks 3530
The `core-shell´ structure of the reduced Ga-doped, A-site-deficient titanates 3530
Factors controlling B-site segregation 3531
Conclusion 3533
References 3533
Relevant Websites 3534
Chapter 4.16: Material and Biological Issues Related to the Use of Inorganic Materials at the Bone-Implant Interface 3536
Introduction 3536
Physiology of Bone 3536
Bone Structures and Composition 3536
Mechanical Properties of Bone 3538
Bone Cells and Mineralization 3538
Impaired Bone Mineralization 3539
Inorganic Materials for Bone-Implant Applications 3540
Inorganic Materials 3540
Structure and properties of bioceramics 3541
Bioactivity, Osteoconductivity, and Osteoinductivity of CaP Ceramics 3541
CaP Ceramics Used as Coatings 3542
Coating Techniques 3543
Biological Properties of Inorganic Coatings 3544
Bone Healing Around the Implant Surface 3544
Cellular Response to Bioactive Ceramics 3544
Bone-Bonding to CaP Ceramics 3546
Degradation of CaP Coatings 3546
Conclusion 3547
References 3547
Chapter 4.17:\x0BOne-Dimensional Ni(III) and Pd(III) Mott Insulators 3550
Introduction 3550
Ni(III) MH Complexes 3551
Crystal Structure 3551
Magnetic Properties 3551
Optical Properties 3553
Fabrication of Optical Thin Films by Introducing Long Alkyl Chains 3554
Pd(III) MH Complexes 3555
Stabilization of the PdIII MH State in Ni-Pd Mixed-Metal Complexes, [Ni1-xPdx(chxn)2Br]Br2 3555
Crystal structure of [Ni1-xPdx(chxn)2Br]Br2 3555
IR spectra of [Ni1-xPdx(chxn)2Br]Br2 3555
ESR spectra of [Ni1-xPdx(chxn)2Br]Br2 3556
Optical conductivity spectra of [Ni1-xPdx(chxn)2Br]Br2 3557
x-Ray diffuse scattering of [Ni1-xPdx(chxn)2Br]Br2 3558
Local electronic structure of [Ni1-xPdx(chxn)2Br]Br2 measured by using STM 3559
Stabilization of the PdIII MH State via the Chemical Pressure Acting between Alkyl Chains 3561
Crystal structure of [Pd(en)2Br](C5-Y)2•H2O 3561
ESR spectroscopy 3561
Raman and optical conductivity spectra 3562
Alkyl chain length dependency 3562
Comparison of Metal-to-Metal Distance in Both Systems 3563
Conclusion 3563
Acknowledgment 3564
References 3564
e9780080965291v5 3565
Front Cover 3565
Volume 5: Porous Materials and Nanomaterials 3568
Copyright 3569
Editorial Board 3570
Contributors 3572
Contents 3586
Preface 3600
Volume Editors' Introduction 3602
Part I: Porous Inorganic Materials - 1. Generic Methods for Characterization of Porous Structures and Properties 3604
Chapter 5.01: Diffraction and Spectroscopy of Porous Solids 3604
Introduction 3604
Materials Covered 3605
Ordered Porous Materials 3605
Zeolites and zeotypes 3605
Metal organic frameworks 3605
Ordered mesoporous materials 3606
Photonic crystals 3606
Disordered Porous Material 3606
Scattering and Diffraction Methods 3606
Crystal Structures 3607
Principles of XRD 3607
Single-Crystal Diffraction 3610
Structure solution from single-crystal data 3610
The Patterson method 3610
Powder Diffraction 3610
Structure solution from powder diffraction data 3611
In situ diffraction 3611
Electron Diffraction 3612
Small-Angle Scattering 3614
Small-angle x-ray scattering 3615
Approximation methods 3618
Scattering on photonic crystals 3619
Spectroscopies 3620
IR Spectroscopy 3621
Analysis of surface properties 3622
Analysis of adsorbate/pore orientation 3622
Analysis of diffusion processes 3623
NMR Spectroscopy 3623
Analysis of motion in porous materials on the molecular scale 3624
Pulsed field gradient NMR spectroscopy 3624
129Xe NMR spectroscopy 3624
Interference Microscopy 3625
Conclusion 3625
References 3626
Chapter 5.02: Adsorption Properties 3628
Introduction 3628
Nanoporous System 3628
Vapor and Supercritical Gas 3629
Adsorption, Absorption, and Sorption 3630
Gas-Solid Interaction 3631
Dispersion Interaction 3631
Molecule-Pore Interaction 3631
Contribution of Electrostatic Interaction 3634
Vapor Adsorption 3634
Adsorption Isotherm and Adsorption Mechanism 3634
Type I adsorption isotherm 3634
Type II and III adsorption isotherms 3635
Type IV and V adsorption isotherms 3636
Role of Modeling in Adsorption in Nanopores 3637
Supercritical Gas Adsorption 3638
New Developments in Adsorption 3640
Adsorption of Water Vapor in Hydrophobic Pores 3640
Quantum Effect in Physical Adsorption 3642
Gate Adsorption 3644
Conclusion 3645
Acknowledgment 3645
References 3646
Part I: Porous Inorganic Materials - 2. Design, Synthesis and Properties 3648
Chapter 5.03: Metal-Organic Frameworks 3648
Introduction 3648
Parts of Coordination Frameworks 3650
Metal Ions 3650
Secondary Building Units 3650
Organic Ligands 3650
Metalloligands 3651
Inorganic Counteranions 3651
Guest Molecules 3652
Synthetic Techniques 3652
Solvothermal Methods 3652
Microwave Syntheses 3652
Post-Synthetic Modification 3652
Methods for Controlling Morphologies of PCP Crystals 3654
Techniques for Obtaining PCP Thin Films 3654
Other Techniques 3655
Representative Topologies of Frameworks 3655
CPL Structures 3655
Jungle-Gym-Type Structures 3656
Zeolitic Imidazolate Frameworks 3656
Coordination Polymers with an Interdigitated Structure 3657
PCPs Based on One-Dimensional Frameworks 3657
Porous Functionalities 3657
Storage 3657
Methane 3657
Carbon dioxide 3659
Hydrogen 3659
Water 3660
Acetylene 3660
Separation 3661
Carbon dioxide 3661
Acetylene 3661
Oxygen 3663
Catalysis 3664
Lewis acid catalysis 3664
Brønsted acid catalysis 3664
Base catalysis 3664
Reaction Vessels in Polymer Syntheses 3665
Framework Dynamics 3665
Framework Stability 3666
Combined Functions of Porosities and Magnetic Properties 3666
Conducting PCPs 3667
Other Properties 3670
Composite PCPs 3670
Conclusion 3671
References 3671
Chapter 5.04: Soft Porous Coordination Polymers 3676
Introduction 3676
Podand Effect, Preorganization, Induced Fit, Cooperative Effect, and Dynamic Behavior on Discrete Systems 3677
Sources of Flexibility in Coordination Compounds 3677
Bond elongation and shortening 3677
Bond cleavage and reformation 3678
Bond rotation 3679
Ligand flexibility 3679
H-bonding, electrostatic and van der Waals interactions 3680
Rigidity and Flexibility in Extended Frameworks 3680
Flexible Porous Frameworks 3681
Sponge-like Behavior or Breathing Effect 3682
Sponge-like behavior or breathing effect arising from framework's flexibility 3682
Sponge-like behavior or breathing effect arising from interdigitating or interpenetrating 3685
Bond Cleavage and Reformation 3687
Bond cleavage and reformation of coordination bonds 3687
Bond cleavage and reformation of weak interactions 3688
Rotation of Bridging Ligands 3689
Other Stimuli-Responsive Frameworks (Temperature, Pressure, pH, Electric/Magnetic Field, etc.) 3691
Influence of Framework Flexibility on Selective Adsorption, Catalysis, and Other Properties 3693
Influence of Framework Flexibility on Selective Adsorption 3693
Influence of Framework Flexibility on Catalysis 3697
Influence of Framework Flexibility on Other Properties 3700
Conclusion 3702
References 3703
Chapter 5.05: Zeolites 3706
Introduction 3706
Zeolite Structure 3706
Zeolite Synthesis Mechanisms 3712
Main Factors Affecting the Synthesis Chemistry 3713
Mineralizing Agents and Their Role as Inorganic Structure Directiong Agents (SDAs) 3713
Isomorphic Substitution in Zeolites: Structure-Directing Effect of Heteroatoms in Framework Positions 3714
Organic SDAs 3716
Solvents 3718
New Trends in Zeolite Synthesis 3719
Phosphorus-Containing SDAs 3719
Zeolite Synthesis in Ionothermal Media 3720
Synthesis of Extra-Large Pore Zeolites 3720
Synthesis of Multipore Zeolites 3720
Synthesis of Organic-Free Zeolites 3721
Synthesis of Zeolite Layers 3722
Application of HT Techniques and Data Mining to the Discovery of New Structures 3723
Other Approaches 3723
Zeolite Properties 3725
Adsorption and Separation 3725
Ion Exchange 3726
Catalytic Applications 3727
Reactions catalyzed by acid and basic sites 3728
Redox reactions 3729
Zeolite-based multifunctional catalysts 3729
Conclusion 3729
Acknowledgment 3730
References 3730
Relevant Websites 3734
Chapter 5.06: Mesoporous Silica 3736
Introduction 3736
Preparation of Mesoporous Materials Using Surfactants 3736
Structural Characterization of Mesoporous Silica 3739
Morphological Control of Periodic Mesoporous Silica 3745
Applications Using Periodic Mesoporous Silica 3747
Conclusion 3750
References 3752
Chapter 5.07: Porous Metals and Metal Oxides 3754
Review 3754
Porosity 3754
Synthesis of Porous Metals 3754
Macroporous Metals 3757
Applications of Porous Metals 3757
Synthesis of Porous Metal Oxides 3759
Microporous Materials 3759
Mesoporous Materials 3762
Macroporous Materials 3767
Applications of Porous Metal Oxides 3767
Conclusion 3769
References 3770
Chapter 5.08: Porous Pillared Clays and Layered Phosphates 3772
Clay Minerals 3773
Introduction to Clay Minerals 3773
Surface properties of clay minerals 3773
Surface acidity 3774
Pillared Interalyer Clays: Pillar Chemistry 3774
PILCs: Synthesis 3775
Pore Structure and Porosity 3776
Structure of the Aluminum PILCs 3777
Thermal Stability 3778
Mixed Cation PILCs 3778
Gallium substitutions 3778
Lanthanide substitutions 3778
Silicon-aluminum system 3779
Zirconium-Pillared Clays 3779
Synthesis of Porous Clay Heterostructures 3781
Pillaring of Vermiculites and Micas 3783
Adsorption and Ion-Exchange Properties of PILCs 3783
Chromia and Titania PILCs: Additional Porosity Considerations 3785
Theories of N2 Sorption-Desorption Isotherm Analyses 3786
Acidic Properties of PCH 3788
PILCs as Catalysts 3789
Anionic Clays 3791
Conclusion 3791
Layered M(IV) Phosphates and Phosphonates 3793
In the Beginning 3793
General structure and properties of α- and gamma-M(IV) phosphates 3794
Preparation and Characterization of M(IV) Phosphates 3795
Exfoliation of M(IV) phosphates 3796
Porous Phosphates and Phosphonates Synthesized by Templating and Self-Assembly 3796
Nonionic templates 3797
Pillaring of M(IV) Phosphates by Inorganic Oligomeric Cations 3799
Transition metal oxides 3800
Alumina and related inorganic clusters 3800
Silica and other mixed oxides 3802
Conclusions and general outlook for inorganically pillared phosphates 3803
Pillaring of gamma-M(IV) Phosphates by Topotactic Exchange 3803
Structure of topotactically exchanged gamma-forms of Zr and Ti phosphate 3803
Examples of pillaring gamma-M(IV) phosphates by bisphosphonic acids 3804
Pillared derivatives of gamma-ZrP with rigid and flexible bisphosphonic acids 3804
Direct Pillaring Using Phosphonic Acids with α-M(IV) Phosphates, UMOFs 3805
M(IV) bisphosphonates 3806
Mixed ligand-pillared materials 3806
Functionalization of UMOFs 3808
Selective ion exchange for nuclear waste streams 3809
Future outlook for organically pillared phosphonates, UMOFs 3810
Acknowledgment 3810
References 3810
Chapter 5.09: Chalcogenides and Nonoxides 3816
e9780080965291v6 3906
Front Cover 3906
Volume 6: Homogeneous Catalytic Applications 3908
Copyright 3909
Editorial Board 3911
Contributors 3913
Contents 3927
Preface 3941
Volume Editor’s Introduction 3943
Part 1: Main Catalytic Processes 3945
Chapter 6.01: Carbonylation Reactions 3945
Introduction 3945
Alcohol Carbonylation Reactions 3945
Methanol Carbonylation Using Rhodium and Iridium Catalysts 3945
Rhodium-catalyzed methanol carbonylation 3946
Heterogenized rhodium catalysts 3948
Promotion by phosphane ligands and derivatives 3949
Iridium-catalyzed methanol carbonylation 3954
Catalytic mechanism 3955
Role of promoters 3956
Alternative Approaches 3958
Other Alcohol Carbonylations 3958
Oxidative Carbonylation of Methanol 3959
Hydroxycarbonylation/Alkoxycarbonylation Reactions 3959
Ethene Hydroxycarbonylation/Methoxycarbonylation 3960
Mechanism 3960
Dienes 3961
Alkynes 3962
Co-Polymerization of Carbon Monoxide and Alkenes 3962
Mechanism 3963
Carbonylation of Epoxides/Aziridines 3963
Pauson–Khand Reaction 3964
Conclusion 3965
References 3965
Chapter 6.02: Hydroformylation 3969
Introduction 3969
Commercialized Applications of Rhodium-Catalyzed Hydroformylation 3969
Selectivity of Hydroformylation – The Effect of Phosphorus Ligands 3971
The Stability of Phosphorus Ligands 3976
Hydroformylation in Ionic Liquids 3976
N-Heterocyclic Carbene–Metal Complexes 3980
Water-Soluble Catalytic Systems 3982
Fluorous Phase Catalysis 3988
Asymmetric Hydroformylation 3988
Conclusion 3988
References 3988
Chapter 6.03: Cross-Coupling Reactions 3991
Introduction 3991
Cross-Coupling Reactions 3992
The Kumada–Tamao–Corriu Reaction 3992
Discovery and definition 3992
Development in different electrophiles 3992
Mechanistic studies 3997
Applications in organic synthesis 3997
Perspective 3998
The Negishi Reaction 3998
Discovery and definition 3998
Development in different electrophiles 3998
Mechanistic studies 4001
Applications in organic synthesis 4001
Perspective 4001
The Migita–Kosugi–Stille Reaction 4002
Discovery and definition 4002
Development in different electrophiles 4002
Mechanistic studies 4004
Applications in organic synthesis 4004
Perspective 4005
The Suzuki–Miyaura Reaction 4005
Discovery and definition 4005
Development in different electrophiles 4005
Mechanistic studies 4010
Applications in organic synthesis 4011
Perspective 4011
The Hiyama Reaction 4011
Discovery and definition 4011
Development in different electrophiles 4011
Mechanistic studies 4013
Applications in organic synthesis 4013
Perspective 4013
The Sonogashira Reaction 4014
Discovery and definition 4014
Development in different electrophiles 4014
Mechanistic studies 4016
Applications in organic synthesis 4017
Perspective 4017
Conclusion 4017
References 4017
Chapter 6.04: Selectivity in C—H Functionalizations 4023
Introduction 4023
Some Terms and Definitions 4024
Substrate Selectivity 4024
Product Selectivity 4025
Position Selectivity (Regioselectivity) 4026
Bond Selectivity 4027
Stereoselectivity 4027
About the Reactivity–Selectivity Principle 4028
Selectivity Enhancement in Molecules Containing Directing Groups 4029
Chelate Control (Reactions Proceeding via Cyclometalation) 4029
Molecular Recognition (Functionalization of Remote C―H Bonds) 4029
Enhancement of Selectivity by Constructing Sterical Hindrance Around a Reaction Center of the Metal Complex 4032
Oxidation in Living Cells 4032
Biomimetic Oxidations Based on Porphyrin-Containing Catalysts 4034
Systems Containing Voluminous and Sterically Hindered Reaction Centers 4036
Organometallic Activation on Reaction Centers with Spatial Hindrance 4040
Selective Reactions Proceeding Within Constrained Inorganic and Organic Nano Pores 4043
Conclusion 4045
References 4046
Relevant Website 4048
Chapter 6.05: Olefin Metathesis 4049
General Introduction 4049
Cross Metathesis Reaction 4050
Olefin Types 4050
Self-metathesis 4051
Cross Metathesis 4052
Statistical CM 4052
Selective CM 4052
Ring-Closing Metathesis 4054
Introduction and Mechanism 4054
Formation of Di-, Tri-, and Tetrasubstituted olefins 4055
Ring Size of Formed Product 4057
Ene-Yne Metathesis 4059
Introduction and Mechanism 4059
Applications of Intramolecular Ene-Yne Metathesis 4060
Applications of Intermolecular Ene-Yne Metathesis 4063
Acyclic Diene Metathesis Polymerization 4064
Ring-Opening Metathesis 4066
Ring-Opening Cross Metathesis 4066
Ring-Opening, Ring-Closing Metathesis 4066
Ring-Opening Metathesis Polymerization 4066
Conclusion 4069
Acknowledgment 4069
References 4069
Chapter 6.06: Oligo- and Polymerization of Olefins 4071
Introduction 4072
Polymerization Mechanisms 4072
Coordination Polymerization 4072
General mechanistic overview 4072
Initiation 4073
Alkylation 4073
Generation of \"vacant\" coordination sites 4073
Single component catalysts 4073
Propagation mechanisms 4073
Cationic metal–alkyl complexes, the role of agostic interactions 4073
Role of the anion 4074
Neutral metal–alkyl complexes 4075
Metallacyclic mechanisms including role in selective tri- and tetramerization 4075
Chain termination steps 4077
β-H elimination 4077
β-H transfer to new monomer 4077
Reductive β-H+alkyl elimination 4077
Chain transfer to other reagents 4077
Living polymerization 4077
Olefin Metathesis (Carbene) Mechanisms 4078
Ring Ring-opening metathesis polymerization 4078
Acyclic diene metahesis polymerization 4078
Green–Rooney mechanism 4079
Cationic Polymerization 4080
Anionic Polymerization 4080
Radical Polymerization 4081
Organometallic radical polymerization 4081
Atom transfer radical polymerization 4082
Control Over Polymer Structure 4082
Linear Oligo- and Polymers 4082
High-density polyethylene 4082
Stereo and tacticity control of α-olefin polymers 4082
Branched Polymers and Copolymers 4084
Branched polymers from homo-polymerization 4084
Branched polymers from copolymerization 4084
Block-copolymerization 4084
Cyclic Polymers 4085
Control of Molecular Weight 4085
Oligomerization 4086
Dimerization 4086
Selective trimerization 4086
Selective tetramerization 4086
Catalysts by Metal Center 4087
Main Group Metals (Including Group 12) 4087
Group 3 (Including Lanthanides) 4087
Group 4 4087
Metallocenes 4087
Half-metallocenes 4087
Non-metallocenes 4088
Group 5 4088
Group 6 4089
Group 7 4090
Group 8 4090
Group 9 4091
Group 10 4091
Group 11 4091
Co-Catalysts, Activators, and Promoters 4092
Methylalumoxane 4092
Other Aluminum Alkyl Compounds 4092
Boranes 4092
Brønsted Acids with Weakly Coordinating Anions 4093
Trityl Salts of Weakly Coordinating Anions 4093
Oxidizing Salts of Weakly Coordinating Anions 4093
Oxidizing Additives (Halide Effects) 4093
Nucleating Additives 4093
Monomers for Olefin Polymerization 4093
Ethylene 4093
α-Olefins 4094
Cyclic Olefins and Non-conjugated Dienes 4094
Higher Substituted Olefins 4094
Styrene 4095
Butadienes 4095
CO (for copolymers) 4096
Other Functionalized Monomers 4096
Heterogeneous Polymerization Catalysts 4096
ZN Catalysts 4096
Phillips Catalysts 4096
Conclusion 4097
References 4097
Chapter 6.07: Combining Transition Metal Catalysis and Organocatalysis 4099
Introduction 4099
Combining a Transition Metal Complex and an Aminocatalyst 4099
α-Alkylation of Carbonyl Compounds 4100
α-Allylic alkylation 4100
α-Propargylic alkylation 4101
α-Alkylation 4102
α-Trifluoromethylation 4102
α-Benzylation 4102
α-Arylation of Carbonyl Compounds 4103
Carbocyclization of Formyl Alkynes 4103
Michael Addition Reactions 4103
Aldol Reactions 4104
Inverse-Electron-Demand Hetero-Diels–Alder Reaction 4104
Cross-Dehydrogenative Coupling Reactions 4105
Cascade Reactions 4105
Addition/cyclization cascade 4105
Hydroformylation-initiated cascades 4106
Cascade carbo-carbonylation 4107
Multicomponent or One-Pot cascade reactions 4108
Combining a Transition Metal Complex and a Brønsted Acid 4109
Combining a Transition Metal Complex and a Stronger Brønsted Acid 4109
Reductive enyne coupling 4109
Asymmetric alkynylation of imines 4110
Asymmetric reductive amination 4110
α-Allylation of α-branched aldehydes 4110
Mannich-type reaction 4111
Cascade reactions 4111
Isomerization/C–C bond-forming reactions 4111
Cycloisomerization-based tandem reactions 4112
Multicomponent reactions involving diazo compounds 4112
Olefin cross-metathesis/C–C bond-forming reactions 4114
Asymmetric cascade hydrogenation 4114
Combining a Transition Metal Complex and a Thiourea 4114
Combining a Transition Metal and a Brønsted Base Catalyst 4115
Aza-Henry Reaction 4115
Allylation of Sulfonylimidates 4117
Conia-ene Reaction 4117
Combining a Transition Metal and a Nucleophilic Catalyst 4117
Combining a Transition Metal and a Phase-Transfer Catalyst 4117
Combining a Transition Metal and a N-Heterocyclic Carbene 4117
Conclusion 4118
Acknowledgment 4118
References 4118
Chapter 6.08: Catalytic Oxidation Processes 4121
Basic Principles of Catalytic Oxidation 4122
Foreword 4122
Dioxygen Activation 4122
Metal–Oxygen Complexes 4122
Biomimetic Oxidations 4123
Hydrogen Peroxide and Alkylhydroperoxides 4124
Wacker-Type Oxidation of Alkenes 4124
The Industrial Processes 4124
Chemical basis of the Wacker process 4125
Wacker process operation 4126
Alternative catalyst formulations 4126
Oxidation of Propylene to Acetone 4127
Vinyl Acetate from Ethylene 4127
Unusual Aldehyde Selective Formation Reactions 4129
New Catalytic Systems without Cu(I) as Cocatalyst 4129
Alternative Oxidants 4130
Use of Metals Other Than Pd 4131
Osmium-Catalyzed Dihydroxylation of Alkenes 4131
Examples of natural products synthesis 4132
Examples of pharmaceutical product synthesis 4134
Chemistry of Peroxides 4134
The Halcon and Related Processes 4134
Chemical basis 4136
Process operation 4136
Use of hydrogen peroxide 4137
Other processes involving TS-1 4137
Heterogenized Homogeneous Systems 4138
Polymer-based systems 4139
Silica-based systems 4140
Ship-in-the-bottle systems 4142
Applications in Environmental Cleanup 4144
Examples of Pharmaceutical Product Synthesis 4145
Esomeprazole 4145
ZD3638 4147
ZD2249 4147
OPC-29030 4147
Indinavir 4147
Oxidations with Molecular Oxygen 4148
Cyclohexane Oxidation: On the Way to Adipic Acid 4148
KA oil from cyclohexane 4148
Adipic acid from KA Oil 4149
Related processes 4150
p-Xylene Oxidation to Terephthalic Acid 4150
Ethylene Oxide by Direct Oxidation of Ethylene 4151
Acrolein and Acrylic Acids 4152
AN from Propylene 4154
Maleic Anhydride 4155
Oxidation of Alcohols 4156
Allylic Oxidation of Alkenes with Oxygen and Perester as Terminal Oxidants 4159
Conclusion 4162
References 4163
Part 2: Asymmetric Catalysis 4167
Chapter 6.09: Enantioselective Hydrogenation of C═C and C═X Bonds 4167
Introduction: Access to Industrial Potentially Active Molecules Obtained by Asymmetric Hydrogenation Reactions 4167
Reduction of C═C Bonds 4169
Running Processes 4169
L-DOPA 4169
L-Phenylalanine 4170
Citronellol 4170
(D)-(+)-Biotine and (+)-cis-methyldihydrojasmonate 4171
Processes in Development 4171
Applications of axially chiral biaryl diphosphanes 4171
Application of ferrocenyl-based diphosphane ligands 4173
DUPHOS ligands 4175
Other chiral diphosphanes catalysts for C═C hydrogenation 4175
Reduction of Ketones 4178
Running Processes 4178
Hydrogenation of functionalized ketones 4178
Hydrogenation of unfunctionalized ketones 4179
Processes in Development 4181
Trifluoropropanol 4181
(R)-3-Quinuclidinol 4181
Transfer hydrogenation 4182
Reduction of Imines and Enamines 4183
Imines 4183
Running process 4183
Synthesis of (S)-Metolachlor 4183
Processes in development 4183
Acyclic imine: Sertraline 4183
Cyclic imines 4185
Dextromethorphan 4185
Asymmetric hydrogenation of quinolones and isoquinolines 4185
N-Sulfonylimine substrate 4186
Enamines 4187
Running processes 4187
Synthesis of β-amino acids 4187
Sitagliptin 4187
Processes in development 4188
Almorexant 4188
HIV-integrase inhibitors 4188
Conclusion 4188
References 4189
Chapter 6.10: Asymmetric Cycloaddition Reactions 4193
Introduction 4193
[4+2] Cycloaddition 4193
Diels–Alder Reaction 4193
Hetero-Diels–Alder Reaction 4196
Transition Metal-Catalyzed [4+2] Cycloaddition 4198
[5+2] Cycloaddition 4201
[2+2] Cycloaddition 4201
[2+2+2] Cycloaddition 4202
Generation of Axial Chirality 4204
Generation of Central Chirality 4205
Generation of Planar Chirality 4208
Generation of Helical Chirality 4208
[3+2] Cycloaddition 4209
[4+3] Cycloaddition 4211
Conclusion 4212
References 4212
Chapter 6.11: Chiral Phosphorous Ligands in Asymmetric Catalysis 4215
Introduction 4215
Fundamentals 4216
Chiral Phosphorous Ligands 4217
Chiral Monodentate Phosphorus Ligands (Including Chiral P-Heterocycles) 4217
Monodentate phosphorus ligands containing phosphorus as the stereogenic center 4217
Monodentate phosphorus ligands containing carbon stereogenic center 4218
Monodentate phosphorus ligands containing planar element of chirality 4219
Monodentate p