Additional Information
Book Details
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 phosphorus ligands containing axial element of chirality | 4220 | ||
| Chiral Bidentate and Multidentate Phosphorus Ligands (Diphosphanes and Polyphosphanes, Diphosphites, Diphosphonites, etc.) | 4225 | ||
| Bidentate diphosphane ligands possessing P-stereogenic centers | 4226 | ||
| Bidentate ligands possessing C-stereogenic center(s) | 4227 | ||
| Bidentate phosphorus ligands supported on atropisomeric biaryl backbones | 4234 | ||
| Bidentate phosphorus ligands with planar and mixed planar–central chirality | 4240 | ||
| Chiral phosphorus ligands with further type of element of chirality | 4241 | ||
| Chiral Heterobidentate and Heteromultidentate Ligands | 4241 | ||
| Chiral P-Ligands Used in Biphasic Catalysis (Supercritical, Aqueous, and Fluorous Media, Ionic Solvents) | 4242 | ||
| Conclusion | 4247 | ||
| References | 4247 | ||
| Chapter 6.12: Asymmetric Epoxidation and Sulfoxidation | 4253 | ||
| Asymmetric Epoxidation | 4254 | ||
| Introduction | 4254 | ||
| With Titanium Catalysts – Electrophilic Epoxidation | 4255 | ||
| The SKAE | 4255 | ||
| The Katsuki asymmetric epoxidation reaction with di-μ-oxidotitanium(salalen) and di-μ-oxidotitanium(salan) complexes | 4257 | ||
| With Manganese Catalysts | 4265 | ||
| Jacobsen–Katsuki monometallic Oxo-Mn(III) complexes | 4265 | ||
| Other Oxo-Mn complexes | 4272 | ||
| Mn(III)–porphyrin oxo complexes | 4272 | ||
| Mn(II) complexes | 4273 | ||
| Mn(III)–Mn(III) and Mn(III)–Mn(IV) dinuclear complexes | 4276 | ||
| With Ruthenium Catalysts | 4277 | ||
| With ruthenium(II) Schiff base and salen catalysts | 4277 | ||
| With ruthenium(III) catalysts containing oxazoline units | 4278 | ||
| With ruthenium(III) catalysts containing pyridine-based ligands | 4278 | ||
| With ruthenium(II) catalysts containing PNNP ligands | 4280 | ||
| Ru–porphyrin oxo complexes | 4281 | ||
| With Iron Catalysts | 4282 | ||
| Fe(III)-diamino and dipyridyl oxo complexes | 4282 | ||
| Fe(III)–porphyrin oxo complexes | 4285 | ||
| With Molybdenum Catalysts | 4285 | ||
| With oxodiperoxomolybdenum(VI) catalysts | 4285 | ||
| With dioxomolybdenum catalysts | 4286 | ||
| With oxomolybdenum–porphyrin catalysts | 4288 | ||
| With Vanadium Catalysts | 4288 | ||
| With vanadium alkyl peroxide catalysts bearing chiral hydroxamic acid ligands | 4289 | ||
| For allylic alcohol substrates | 4289 | ||
| With vanadium(V) oxo–peroxo complexes | 4297 | ||
| With Chromium Catalysts | 4297 | ||
| With Oxorhenium Catalysts | 4299 | ||
| With Zirconium, Hafnium, Nobium and Ytterbium – Nucleophilic Epoxidation | 4300 | ||
| With Platinum, Gold, and Zinc Catalysts – Nucleophilic Epoxidation | 4308 | ||
| With Alkaline Earth Oxides | 4309 | ||
| Asymmetric Sulfoxidation | 4309 | ||
| Introduction | 4309 | ||
| With Titanium and Zirconium Catalysts | 4311 | ||
| With Vanadium Catalysts | 4315 | ||
| With Manganese Catalysts | 4316 | ||
| With Molybdenum and Tungsten Catalysts | 4317 | ||
| With Iron, Ruthenium, and Aluminum Catalysts | 4318 | ||
| Conclusion | 4323 | ||
| References | 4323 | ||
| Chapter 6.13: Asymmetric Carbonylations | 4327 | ||
| Introduction | 4327 | ||
| Rh-Catalyzed Asymmetric Hydroformylation of Alkenes Using Phosphorus Donor Ligands | 4328 | ||
| Introduction | 4328 | ||
| Rh-Catalyzed Hydroformylation Mechanism | 4329 | ||
| Rh-Catalyzed Asymmetric Hydroformylation of Monosubstituted Alkenes | 4329 | ||
| 1,3-Diphosphite ligands | 4330 | ||
| Phosphane–phosphite ligands | 4331 | ||
| Bisphospholane ligands | 4333 | ||
| Bis-phosphonite ligands | 4334 | ||
| Monodentate phosphorus-based ligands | 4334 | ||
| Rh-Catalyzed Asymmetric Hydroformylation of Disubstituted Alkenes | 4335 | ||
| Linear 1,2-disubstituted alkenes | 4336 | ||
| Monocyclic 1,2-disubstituted alkenes | 4337 | ||
| Bicyclic 1,2-disubstituted alkenes | 4338 | ||
| 1,1'-Disubstituted alkenes | 4339 | ||
| Other Substrates | 4340 | ||
| α,β-Unsaturated amides, 1,3-dienes, N-vinyl carboxamides, allyl carbamates, and allyl ethers | 4340 | ||
| Scaffolding ligands | 4340 | ||
| Conclusions | 4342 | ||
| Asymmetric Pd-Catalyzed Alkoxycarbonylation of Vinyl Arenes | 4342 | ||
| Introduction | 4342 | ||
| Mechanism | 4343 | ||
| Asymmetric Alkoxycarbonylation of Vinyl Arenes | 4344 | ||
| Bidentate diphosphanes | 4344 | ||
| Hemilabile P–N ligands | 4345 | ||
| Monodentate ligands | 4345 | ||
| Asymmetric Bis-Alkoxycarbonylation of Vinyl Arenes | 4346 | ||
| Conclusions | 4347 | ||
| Asymmetric CO/Olefin Co- and Terpolymerization | 4347 | ||
| Introduction | 4347 | ||
| Mechanism | 4348 | ||
| Asymmetric copolymerization of CO with propene and aliphatic 1-alkenes | 4349 | ||
| Asymmetric copolymerization of CO with vinyl arenes | 4350 | ||
| Modular N–N' ligands for the copolymerization of CO and styrene | 4350 | ||
| Asymmetric CO/Olefins Terpolymerization | 4351 | ||
| Conclusion | 4351 | ||
| References | 4352 | ||
| Chapter 6.14: Asymmetric Cyanation Reactions | 4357 | ||
| Introduction | 4357 | ||
| Sources of Cyanide | 4358 | ||
| Asymmetric Cyanation of Aldehydes and Ketones | 4359 | ||
| Asymmetric Cyanation of Aldehydes | 4359 | ||
| Catalytic System Based on Titanium | 4360 | ||
| Titanium-chiral alcohol complexes | 4360 | ||
| Titanium-based chiral C2-symmetric complexes | 4360 | ||
| Synthesis of Enantiopure Cyanohydrin Ester | 4361 | ||
| Asymmetric Cyanoformylation of Aldehydes | 4362 | ||
| Mechanistic studies on [(salen) TiO]2 | 4364 | ||
| Other C2-symmetric salen complexes | 4365 | ||
| Immobilized C2-symmetric salen-derived catalysts | 4365 | ||
| C1-symmetric ligand for cyanation reaction | 4365 | ||
| Titanium BINOL-based complexes | 4366 | ||
| Amide-based ligands with titanium | 4366 | ||
| Bifunctional catalysts | 4367 | ||
| Aluminum-Based Catalytic System | 4368 | ||
| Pyridine-2,6-Bisoxazoline (pybox)-Based Complexes | 4370 | ||
| Vanadium-Based Catalysts | 4371 | ||
| Tin Complexes | 4372 | ||
| Yttrium Complexes | 4372 | ||
| Bismuth Catalysts | 4372 | ||
| Lanthanide Complexes | 4372 | ||
| Manganese-Based Catalysts | 4372 | ||
| Cobalt-Based System | 4372 | ||
| Chiral Base Catalysts | 4372 | ||
| Alternative Sources of Cyanides | 4373 | ||
| Asymmetric Cyanation of Ketones | 4376 | ||
| Nonmetal Synthetic/Semisynthetic Organic Compounds | 4381 | ||
| Asymmetric Strecker Reactions | 4383 | ||
| Acid-Catalyzed Reactions | 4385 | ||
| Base-Catalyzed Reactions | 4385 | ||
| Metal-Complex-Catalyzed Asymmetric Strecker Reactions | 4387 | ||
| Olefin Cyanation | 4393 | ||
| Cyanation Reaction with Enzyme | 4396 | ||
| Conclusion | 4397 | ||
| Acknowledgment | 4398 | ||
| References | 4398 | ||
| Chapter 6.15: Supramolecular Catalysis | 4401 | ||
| Introduction | 4401 | ||
| Construction of Ligands via Supramolecular Interactions | 4401 | ||
| Lewis Acid–Lewis Base Interactions | 4402 | ||
| Modification of monodentate ligands | 4402 | ||
| Construction of bidentate ligands using Lewis acid–Lewis base interactions | 4402 | ||
| Bidentate Ligands Based on Ionic Interactions | 4405 | ||
| Bidentate Ligands through Hydrogen-Bonding Interactions | 4406 | ||
| Secondary phosphane oxides as supramolecular building blocks | 4406 | ||
| Use of hydrogen bonding in the construction of the catalyst backbone | 4408 | ||
| Catalysis Using Substrate–Ligand Interactions | 4415 | ||
| Asymmetric Reactions in the Interior of Molecular Cavities | 4417 | ||
| Chiral Cavities of Metal-Mediated Receptors | 4417 | ||
| Molecular Cavities for Asymmetric Organocatalysis | 4424 | ||
| Bio-Inspired Molecular Cavities: Synthetic Hybrids between Biomacromolecules and Organometallic Catalysts | 4425 | ||
| Conclusion | 4428 | ||
| References | 4428 | ||
| Chapter 6.16: Stereoselective C—N Bond Formation by Hydroamination of Olefins, Alkyne, Allenes, and Dienes | 4431 | ||
| Introduction | 4431 | ||
| Late-Transition-Metal-Catalyzed Hydroaminations | 4431 | ||
| Bicyclic Alkene Insertions into M—N Bonds | 4431 | ||
| Diene Hydroamination | 4433 | ||
| Vinylarene Hydroamination | 4433 | ||
| Intramolecular Hydroamination/Cyclization | 4434 | ||
| Gold-Catalyzed Allene Hydroamination | 4437 | ||
| Enantioselective Gold-Catalyzed Alkene and Diene Hydroaminations | 4440 | ||
| Michael-Type Additions of Amines to α,β-Unsaturated Carbonyl Compounds | 4441 | ||
| Rare-Earth-Element-Catalyzed Stereoselective Hydroaminations | 4443 | ||
| Diastereoselective Rare-Earth-Mediated Cyclizations of Amino Alkenes | 4444 | ||
| Diastereoselective Cyclizations of Amino Allenes | 4448 | ||
| Diastereoselective Cyclizations of Amino Dienes | 4450 | ||
| Enantioselective, Rare-Earth-Catalyzed Hydroaminations of Olefins | 4451 | ||
| Zirconium-Catalyzed Stereoselective Hydroaminations | 4457 | ||
| Enantioselective Amino Alkene Cyclizations | 4457 | ||
| Enantioselective Amino Allene Cyclizations | 4459 | ||
| Main-Group Element-Catalyzed Enantioselective Hydroaminations | 4460 | ||
| Conclusion | 4462 | ||
| Acknowledgment | 4462 | ||
| References | 4462 | ||
| Part 3: Homogeneous Catalysis and Green Chemistry | 4465 | ||
| Chapter 6.17: Application of Nontoxic Iron Salts in Oxidative C—C Coupling Reactions | 4465 | ||
| Introduction | 4465 | ||
| Csp―Csp Oxidative Coupling Reactions | 4465 | ||
| Csp―Csp2 Oxidative Coupling Reactions | 4465 | ||
| Csp―Csp3 Oxidative Coupling Reactions | 4466 | ||
| Csp2―Csp2 Oxidative Coupling Reactions | 4468 | ||
| Oxidative Couplings between Arenes | 4468 | ||
| Oxidative couplings of phenol and naphthol derivatives | 4468 | ||
| Direct oxidative couplings with aryl metal nucleophiles | 4470 | ||
| Oxidative couplings of heteroarenes | 4472 | ||
| Synthesis of polycyclic aromatic hydrocarbons | 4474 | ||
| Couplings between Arenes/Alkenes and Alkenes | 4474 | ||
| Csp2―Csp3 Oxidative Coupling Reactions | 4475 | ||
| Csp3―Csp3 Oxidative Coupling Reactions | 4479 | ||
| Conclusion | 4485 | ||
| References | 4490 | ||
| Chapter 6.18: Iron Complexes as Substitutes for Toxic Metals in Asymmetric Synthesis | 4493 | ||
| Introduction | 4493 | ||
| Enantioselective Oxidation | 4493 | ||
| Enantioselective Oxidation of Olefins | 4493 | ||
| Enantioselective Oxidation of Sulfides to Sulfoxides | 4496 | ||
| Miscellaneous Enantioselective Oxidation Reactions | 4498 | ||
| Iron-Catalyzed Asymmetric Reduction Reaction | 4499 | ||
| Iron-Catalyzed Asymmetric Hydrogenations | 4499 | ||
| Iron-Catalyzed Asymmetric Transfer Hydrogenations | 4501 | ||
| Iron-Catalyzed Asymmetric Hydrosilylations | 4503 | ||
| Conclusion | 4504 | ||
| References | 4505 | ||
| Chapter 6.19: From Carbon Dioxide to Valuable Products under Homogeneous Catalysis | 4507 | ||
| Introduction | 4507 | ||
| CO2 Control Technologies: Efficiency Technologies Versus Capture of CO2 from Flue Gases and Industrial Processes | 4507 | ||
| Disposal or Use of Captured CO2? | 4508 | ||
| The Utilization Option: Technological, Chemical, and Enhanced Biological Utilization | 4508 | ||
| Catalysis at Work in CO2 Conversion | 4508 | ||
| Fixation of the Entire CO2 Molecule | 4509 | ||
| Reaction with Olefins | 4509 | ||
| Reaction with Dienes | 4510 | ||
| Reaction with Alkynes | 4513 | ||
| Reaction with Active C–H Bonds | 4513 | ||
| Synthesis and Decomposition of Formic Acid | 4514 | ||
| Carbon dioxide homogeneous hydrogenation to afford formate salts | 4515 | ||
| Decomposition of formic acid to afford dihydrogen and CO2 | 4517 | ||
| Synthesis of Carbamates and Polyurethans via Reaction with Amines | 4517 | ||
| Synthesis of Acyclic Carbonates via Carboxylation of Alcohols | 4519 | ||
| Synthesis of Cyclic Carbonates | 4522 | ||
| CO2 as Co-monomer in the Synthesis of Polycarbonates | 4523 | ||
| Comparison with Enzymatic Carboxylations | 4523 | ||
| Reduction to CO | 4524 | ||
| Reduction to Methanol, Methane, or Cn Species | 4525 | ||
| Conclusion | 4527 | ||
| References | 4527 | ||
| Chapter 6.20: Hydrogen Generation from Formic Acid and Alcohols | 4531 | ||
| Introduction | 4531 | ||
| Hydrogen Generation from Formic Acid | 4533 | ||
| Hydrogen Generation from Formic Acid Amine Adducts | 4533 | ||
| Hydrogen Generation from Formic Acid in Ionic Liquids | 4534 | ||
| Hydrogen Generation from Formates or Formic Acid Base Mixtures | 4535 | ||
| Application of Nonprecious Metals in the Hydrogen Generation from Formic Acid | 4537 | ||
| Hydrogen Generation from Alcohols | 4538 | ||
| Synthetic Aspects of the Acceptorless Alcohol Dehydrogenation | 4538 | ||
| Alcohols to aldehydes and ketones | 4539 | ||
| Alcohols to esters | 4540 | ||
| Alcohols to amides | 4541 | ||
| Miscellaneous | 4541 | ||
| Hydrogen Generation from Alcohols with Respect to Energetic Application | 4542 | ||
| Conclusion | 4544 | ||
| References | 4545 | ||
| Chapter 6.21: Catalytic Asymmetric C–C Bond Formation in Aqueous Medium | 4549 | ||
| Introduction | 4549 | ||
| Allylic Substitution Reaction | 4549 | ||
| Diels–Alder Reaction | 4549 | ||
| Aldol Reaction and Hydroxymethylation | 4551 | ||
| 1,4-Conjugate Additions | 4557 | ||
| Allylation | 4559 | ||
| Mannich-Type Reaction | 4563 | ||
| Propargylation | 4563 | ||
| Ring-Opening Reactions of meso-Epoxides | 4563 | ||
| Nazarov-Type Reaction | 4565 | ||
| Ene Reaction | 4566 | ||
| Pauson–Khand-Type Reaction in Water | 4566 | ||
| Conclusion | 4566 | ||
| References | 4567 | ||
| Chapter 6.22: Sustainable Asymmetric Oxidations | 4569 | ||
| Introduction | 4569 | ||
| Catalytic Asymmetric Epoxidations with H2O2 and O2 | 4570 | ||
| Manganese Systems | 4570 | ||
| Iron and Ruthenium Systems | 4572 | ||
| Titanium Systems | 4577 | ||
| Systems Based on Other Metals | 4579 | ||
| Catalytic Enantioselective Sulfoxidations with H2O2 and O2 | 4581 | ||
| Vanadium Systems | 4581 | ||
| Titanium Systems | 4586 | ||
| Iron Systems | 4588 | ||
| Systems Based on Other Metals | 4589 | ||
| Miscellaneous Catalytic Asymmetric Oxidations with H2O2 and O2 | 4592 | ||
| cis-Dihydroxylations | 4592 | ||
| Baeyer–Villiger Oxidations | 4593 | ||
| Oxidative Kinetic Resolution of Secondary Alcohols | 4594 | ||
| Sustainable Organocatalytic Oxidations: An Alternative? | 4598 | ||
| Organocatalytic Epoxidation with H2O2 | 4598 | ||
| Miscellaneous Organocatalytic Oxidations with H2O2 | 4601 | ||
| Conclusion | 4603 | ||
| References | 4604 | ||
| Chapter 6.23: Cobalt(II) Carboxylate Chemistry and Catalytic Applications | 4609 | ||
| Introduction | 4609 | ||
| Structures of Cobalt(II) Carboxylate Complexes | 4610 | ||
| Mononuclear Complexes | 4610 | ||
| Dinuclear Complexes | 4610 | ||
| Trinuclear Complexes | 4612 | ||
| Tetranuclear Complexes | 4613 | ||
| Penta- and Hexanuclear Complexes | 4614 | ||
| Hepta- and Octanuclear Complexes | 4615 | ||
| Higher Polynuclear Complexes | 4616 | ||
| Polymeric Complexes | 4618 | ||
| Catalysis | 4618 | ||
| Catalytic Oxidation | 4618 | ||
| Oxidative Dehydrogenation | 4622 | ||
| Carboxylation and Carbonylation | 4623 | ||
| Methoxycarbonylation | 4623 | ||
| Decomposition of Peroxides | 4624 | ||
| Polymerization | 4624 | ||
| Hydrogenation | 4625 | ||
| Drying of Alkyd Resins | 4625 | ||
| Alcohol Homologation | 4625 | ||
| Conclusion | 4625 | ||
| References | 4626 | ||
| Part 4: Biologically Inspired Catalytic Processes | 4629 | ||
| Chapter 6.24: Biocatalysis by Metalloenzymes | 4629 | ||
| Introduction | 4629 | ||
| Iron-Containing Enzymes | 4630 | ||
| Heme Peroxidase | 4630 | ||
| Overview of catalytic cycle | 4630 | ||
| Potential applications of heme peroxidases | 4631 | ||
| Oxidation of activated C–H bond from aromatics | 4631 | ||
| Oxidation of activated C–H bond from alkenes | 4635 | ||
| Heteroatom oxidation | 4636 | ||
| Activation of halogens | 4636 | ||
| Cytochrome P450 | 4640 | ||
| Overview of catalytic cycle | 4641 | ||
| Potential applications of cytochrome P450 enzymes | 4642 | ||
| Activation of alkanes | 4643 | ||
| Activation of saturated C–H bond for fine chemicals or drugs | 4645 | ||
| Oxidation of insaturated C–H bond | 4646 | ||
| Other reactions: dealkylation, deamination, sulfoxidation | 4647 | ||
| Nonheme Iron Oxygenases | 4647 | ||
| Aromatic dioxygenase | 4648 | ||
| Nitroarene dioxygenase | 4648 | ||
| Methane and alkane monooxygenases | 4648 | ||
| Enzymes Containing Copper | 4648 | ||
| Laccase | 4649 | ||
| Tyrosinase | 4653 | ||
| Methane Monooxygenase (Particulate Form) | 4660 | ||
| Enzymes Containing Cobalt | 4662 | ||
| Nitrile Hydratase | 4662 | ||
| Enzymes Containing Zinc | 4665 | ||
| L-Amino Acylase | 4665 | ||
| Aminopeptidase | 4668 | ||
| Alcohol Dehydrogenase | 4671 | ||
| Vanadium-Containing Enzymes | 4674 | ||
| Conclusion | 4675 | ||
| Acknowledgment | 4675 | ||
| References | 4675 | ||
| Relevant Website | 4679 | ||
| Chapter 6.25: Biomacromolecules as Ligands for Artificial Metalloenzymes | 4681 | ||
| Introduction | 4681 | ||
| Design of Artificial Metalloenzymes | 4681 | ||
| Proteins as Biological Scaffolds | 4682 | ||
| Supramolecular anchoring | 4682 | ||
| Dative anchoring | 4684 | ||
| Covalent anchoring | 4691 | ||
| DNA and RNA as a Biological Scaffold | 4695 | ||
| Supramolecular anchoring | 4696 | ||
| Covalent anchoring | 4699 | ||
| Conclusion | 4701 | ||
| References | 4703 | ||
| Chapter 6.26: Hydrocarbon Oxidations Catalyzed by Bio-Inspired Nonheme Iron and Copper Catalysts | 4707 | ||
| Introduction | 4707 | ||
| Background | 4707 | ||
| Hydrocarbon Oxidations in Biological Systems | 4707 | ||
| Biomimetic Oxidation of Aliphatic C―H Bonds | 4708 | ||
| Mechanistic Considerations | 4708 | ||
| Iron-Catalyzed C―H Bond Oxidation | 4709 | ||
| Copper-Catalyzed C―H Bond Oxidation | 4713 | ||
| Biomimetic Alkene Oxidation | 4714 | ||
| Olefin Epoxidation | 4714 | ||
| Olefin cis-Dihydroxylation | 4717 | ||
| Asymmetric Oxidation | 4718 | ||
| Conclusion | 4719 | ||
| Acknowledgment | 4720 | ||
| References | 4720 | ||
| Chapter 6.27: Artificial Metalloproteases and Metallonucleases | 4723 | ||
| Artificial Metalloproteases | 4723 | ||
| Artificial Metalloprotease Analogs | 4724 | ||
| Oxidative cleavage of peptides or proteins | 4724 | ||
| Oxidation of proteins | 4724 | ||
| Oxidative decarboxylation of oligopeptides | 4725 | ||
| Photo-induced cleavage of proteins | 4725 | ||
| Hydrolytic cleavage of proteins in the presence of oxidizing agents | 4725 | ||
| Hydrolysis of activated analogs of peptides | 4725 | ||
| Artificial Metalloproteases with High Affinity for Products | 4725 | ||
| Catalytic Centers of Artificial Metalloproteases | 4726 | ||
| Mononuclear metal centers | 4726 | ||
| Multinuclear metal centers | 4727 | ||
| Artificial Metalloproteases Containing Organic Pendants as Substrate-Binding Sites | 4728 | ||
| Artificial metalloproteases with enhanced affinity for proteins | 4728 | ||
| Artificial metalloproteases with site selectivity | 4730 | ||
| Substrate-selective artificial metalloproteases | 4730 | ||
| Selective cleavage of target proteins | 4730 | ||
| Selective cleavage of oligomers of amyloidogenic oligopeptides or proteins | 4731 | ||
| Artificial Metallonucleases | 4732 | ||
| Artificial Metallonuclease Analogs | 4734 | ||
| Oxidative cleavage of DNA | 4734 | ||
| Photo-induced cleavage of DNA | 4735 | ||
| Hydrolytic cleavage of DNA in the presence of oxidizing agents | 4735 | ||
| Hydrolysis of activated analogs of RNA and DNA | 4735 | ||
| Artificial Metalloribonucleases | 4735 | ||
| Catalytic centers for artificial metalloribonucleases | 4735 | ||
| Mononuclear metal centers | 4735 | ||
| Multinuclear metal centers | 4736 | ||
| Artificial metalloribonucleases with sequence selectivity | 4737 | ||
| Metal centers acting with conjugated recognition sites | 4737 | ||
| Metal centers acting with separately added recognition sites | 4740 | ||
| Artificial Metallodeoxyribonucleases | 4740 | ||
| Catalytic centers for artificial metallodeoxyribonucleases | 4740 | ||
| Mononuclear metal centers | 4740 | ||
| Multinuclear metal centers | 4741 | ||
| Artificial metallodeoxyribonucleases with enhanced affinity for DNA | 4742 | ||
| Artificial metallodeoxyribonucleases with sequence selectivity | 4744 | ||
| Conclusion | 4745 | ||
| References | 4746 | ||
| e9780080965291v7 | 4748 | ||
| e9780080965291v8 | 5400 | ||
| Front Cover | 5400 | ||
| Volume 8: Coordination and Organometallic Chemistry | 5403 | ||
| Copyright | 5404 | ||
| Editorial Board | 5405 | ||
| Contributors | 5407 | ||
| Contents | 5421 | ||
| Preface | 5435 | ||
| Volume Editor´s Introduction | 5437 | ||
| Coordination and Organometallic Chemistry | 5439 | ||
| Chapter 8.01: Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies | 5439 | ||
| Introduction | 5439 | ||
| Metallosupramolecular Chemistry | 5439 | ||
| Hard and Soft Acids and Bases | 5440 | ||
| The Chelate Effect | 5440 | ||
| The Macrocyclic and Cryptate Effects | 5440 | ||
| Metal-Binding Domains | 5441 | ||
| The Synthetic Toolkit: Favored Conjugation Reactions | 5441 | ||
| The Synthetic Organic Chemistry | 5441 | ||
| The Suzuki reaction | 5441 | ||
| The Stille reaction | 5443 | ||
| Sonogashira coupling | 5443 | ||
| Click chemistry | 5443 | ||
| Schiff base chemistry | 5443 | ||
| Grubbs´ catalyzed ring-closing metathesis | 5443 | ||
| Template Reactions | 5444 | ||
| Ligand Design for Macrocycles | 5445 | ||
| Ligand Design for Coordination Polymers and Networks | 5448 | ||
| Ligand Design for Metallopolygons | 5451 | ||
| Taking Metallosquares into Three Dimensions through Ligand Design | 5454 | ||
| Metalloligand Design | 5454 | ||
| Ligand Design for Metal-Ion Extraction | 5458 | ||
| Introduction | 5458 | ||
| Copper | 5460 | ||
| Gold, Palladium, and Platinum | 5462 | ||
| Cobalt, Nickel, and Zinc | 5463 | ||
| f-Block Metal Ions | 5463 | ||
| p-Block Metal Ions | 5464 | ||
| Conclusion | 5464 | ||
| References | 5464 | ||
| Chapter 8.02: Coordination Self-assembly: Structure and Function Updated | 5469 | ||
| Introduction | 5469 | ||
| Structure | 5470 | ||
| Molecular Polygons | 5470 | ||
| 3D Molecular Ensembles | 5471 | ||
| Molecular prisms | 5471 | ||
| Capped prisms | 5471 | ||
| Open prisms | 5472 | ||
| Interlocked structures | 5473 | ||
| Molecular polyhedra | 5474 | ||
| Tetrahedra | 5474 | ||
| Cubes | 5477 | ||
| Octahedra | 5477 | ||
| Cuboctahedra | 5478 | ||
| Rhombicuboctahedra | 5479 | ||
| Other polyhedra | 5479 | ||
| Function of 3D Self-Assembled Structures | 5480 | ||
| Molecular Recognition | 5480 | ||
| Charged guests | 5480 | ||
| Cationic guests | 5480 | ||
| Anionic guests | 5480 | ||
| Neutral guests | 5480 | ||
| Molecular recognition by functionalized compounds | 5482 | ||
| Applications based on molecular recognition | 5483 | ||
| Sensing | 5483 | ||
| Storage and release | 5483 | ||
| Recognition and conformational control of peptides and nucleotides | 5483 | ||
| Other applications | 5483 | ||
| Reactions and Catalysis | 5485 | ||
| Unusual reactivity and selectivity | 5485 | ||
| [2+2] Alkene photodimerization | 5485 | ||
| [2+2] Cross-photoaddition of alkenes | 5485 | ||
| [2+4] Diels-Alder reactions | 5486 | ||
| Other reactions | 5486 | ||
| Product and intermediate stabilization | 5488 | ||
| Catalysis | 5489 | ||
| Encapsulation of catalysts within self-assembled hosts | 5489 | ||
| Palladium catalysis by supramolecular complexes | 5489 | ||
| Catalysis by supramolecular complexes containing no active sites | 5489 | ||
| Cavity templated reactions | 5490 | ||
| Physical Properties | 5490 | ||
| Redox properties | 5490 | ||
| Host-guest energy transfer | 5490 | ||
| Magnetic properties | 5491 | ||
| Other properties | 5491 | ||
| Conclusion | 5491 | ||
| References | 5491 | ||
| Chapter 8.03: Noncovalent Metal-Metal Interactions | 5497 | ||
| Introduction | 5497 | ||
| d8-d8 Metal•••Metal Interactions | 5497 | ||
| Rhodium(I) | 5498 | ||
| Iridium(I) | 5504 | ||
| Palladium(II) | 5505 | ||
| Platinum(II) | 5507 | ||
| Gold(III) | 5522 | ||
| d10-d10 Metall•••Metal Interactions | 5524 | ||
| Copper(I) | 5524 | ||
| Silver(I) | 5532 | ||
| Gold(I) | 5539 | ||
| Mercury(II) | 5553 | ||
| Heterometallic Metal•••Metal Interactions | 5555 | ||
| Double Salts | 5555 | ||
| Dinuclear Frameworks | 5556 | ||
| Metal Clusters | 5556 | ||
| Others | 5559 | ||
| Conclusion | 5562 | ||
| Acknowledgments | 5562 | ||
| References | 5562 | ||
| Chapter 8.04: Fundamentals, Principles, and Concepts of Molecular Magnetism and Spintronics | 5569 | ||
| Introduction | 5570 | ||
| Molecular Magnetism | 5570 | ||
| Definition | 5570 | ||
| Relations with Theoretical Aspects of Other Disciplines | 5571 | ||
| Chemistry | 5571 | ||
| Physics | 5571 | ||
| Biology | 5571 | ||
| Fundamental Problems | 5571 | ||
| Theoretical Description of Atoms and Molecules | 5571 | ||
| Atoms | 5572 | ||
| Molecules | 5573 | ||
| Theoretical Description of Open-Shell Molecules | 5575 | ||
| Theoretical Description of Transition Metal Complexes | 5576 | ||
| Coordination complexes | 5576 | ||
| Crystal field model | 5576 | ||
| MO model | 5577 | ||
| Octahedral complex ML6, (sigma type ligand orbitals, M=Fe3+, electronic configuration d5) | 5578 | ||
| Spin crossover | 5579 | ||
| The Spin and the Molecule | 5583 | ||
| Electron and spin | 5583 | ||
| The spin in the molecule, charge and spin densities | 5583 | ||
| Spin delocalization, spin polarization | 5584 | ||
| Phenomenological Models | 5584 | ||
| Spin Hamiltonian | 5584 | ||
| Heisenberg-Dirac-van Vleck SH | 5585 | ||
| Spin-orbit coupling and zero-field splitting | 5586 | ||
| Effective Hamiltonian Theory | 5586 | ||
| Exchange | 5586 | ||
| Electron Configurations and States | 5587 | ||
| Pioneering Fundamental Contributions | 5587 | ||
| Heisenberg, Dirac, Kramers, Anderson | 5587 | ||
| The Goodenough-Kanamori rules | 5590 | ||
| Molecular Heuristic Approaches | 5590 | ||
| HL model, nonorthogonal orbitals | 5590 | ||
| HL model, orthogonalized orbitals | 5592 | ||
| HM model, orthogonalized delocalized orbitals | 5592 | ||
| Interaction through a bridge in an A-X-B entity, superexchange | 5593 | ||
| Superexchange | 5594 | ||
| Influence of bridge's energy and geometry, qualitative conclusions | 5595 | ||
| Exchange through a molecular bridge (oxalate) | 5595 | ||
| Exchange in a nonsymmetric AB molecule | 5597 | ||
| Interaction between several unpaired electrons: concept of orbital pathway | 5597 | ||
| HL model | 5597 | ||
| HM model | 5598 | ||
| Selected applications | 5598 | ||
| Ferromagnetic coupling in a copper(II)-vanadyl(IV) dinuclear complex | 5598 | ||
| AF interaction between different spins: molecular ferrimagnetism | 5599 | ||
| Exchange through an oxalate bridge with many electrons | 5600 | ||
| Exchange between two electrons through molecular bridges similar to oxalate | 5601 | ||
| Refining the Models | 5601 | ||
| Exchange with Unquenched Orbital Angular Momenta | 5602 | ||
| Exchange in the Presence of Orbital Degeneracy, Frustration, and AS Exchange | 5602 | ||
| Double Exchange | 5603 | ||
| Computational Methods | 5603 | ||
| WFT-based methods | 5603 | ||
| BS approach and DFT | 5605 | ||
| Other computational methods | 5606 | ||
| Magnetic Anisotropy | 5606 | ||
| Multifunctional Molecular Magnetism | 5609 | ||
| Introduction | 5609 | ||
| Coexistence of Magnetism and Other Functions | 5612 | ||
| Interaction Between Magnetism and Another Function | 5613 | ||
| Magnetism and chirality: magnetochiral dichroism | 5613 | ||
| Magnetism and ionic (protonic) conductivity | 5615 | ||
| Physical properties allowed by noncentrosymmetry and their interaction: multiferroics, SHG, MSHG, etc. | 5615 | ||
| Tuning Magnetism Under an External Constraint | 5617 | ||
| Molecular Spintronics | 5618 | ||
| Spintronics: Definition | 5618 | ||
| Tunneling Through Molecule: Kondo Resonance | 5618 | ||
| GMR: Spin Valves | 5619 | ||
| Molecular Spintronics | 5619 | ||
| Quantum Computing | 5621 | ||
| Conclusion | 5622 | ||
| References | 5622 | ||
| Relevant Websites | 5627 | ||
| Chapter 8.05: Cobalt(II) Carboxylate Chemistry and Molecular Magnetism | 5629 | ||
| Introduction | 5630 | ||
| Carboxylate Binding Modes | 5630 | ||
| Cobalt(II) Carboxylate Complexes | 5631 | ||
| Acetate Complexes | 5631 | ||
| Homoleptic acetate complexes | 5631 | ||
| Heteroleptic acetate complexes | 5633 | ||
| Haloacetate Complexes | 5638 | ||
| Triflouroacetate complexes | 5638 | ||
| Trichoroacetate complexes | 5642 | ||
| Dichloroacetate complexes | 5643 | ||
| Chloroacetate complexes | 5644 | ||
| Propionate and Butanate Complexes | 5644 | ||
| Pivalate (Trimethylacetate) Complexes | 5644 | ||
| Benzoate Complexes | 5651 | ||
| Phthalate and Terephthalate Complexes | 5655 | ||
| Fatty Acid Carboxylate Complexes | 5656 | ||
| Phenoxyacetate and Phenoxybutanate Complexes | 5657 | ||
| α,beta-Unsaturated Aliphatic Carboxylate Complexes | 5657 | ||
| α,omega-Dicarboxylate Complexes | 5658 | ||
| Cobalt(II) Carboxylates as SMMs | 5661 | ||
| Conclusion | 5664 | ||
| References | 5664 | ||
| Chapter 8.06: Photochemistry of Metal Carbonyls | 5667 | ||
| Scope and Principles | 5667 | ||
| Excited-State Characters and Assignments of Electronic Spectra | 5669 | ||
| Excited States of Mononuclear Binary Metal Carbonyls | 5669 | ||
| Excited States of Substituted Metal Carbonyls | 5670 | ||
| Gas-Phase Photochemistry and Theory of Photochemistry | 5672 | ||
| Dynamics of Photodissociation from Binary Metal Carbonyls: Mechanism of Prompt Photodissociation | 5672 | ||
| Dynamics of Photodissociation from Substituted Metal Carbonyls | 5675 | ||
| Luminescent Metal Carbonyls and Emission from Equilibrated Excited States | 5676 | ||
| Mechanisms of Photochemistry in Solution | 5677 | ||
| Mononuclear Binary Metal Carbonyls | 5677 | ||
| Binary Di- and Trinuclear Metal Carbonyls in Solution and Matrices | 5679 | ||
| Substituted Mononuclear Metal Carbonyls | 5680 | ||
| Fast and slow CO photodissociation from MLCT states | 5680 | ||
| Formation of sigma-alkane complexes and alkane oxidative addition products | 5682 | ||
| Noble gases as ligands for metal carbonyls | 5684 | ||
| Preferential dissociation of noncarbonyl ligands | 5685 | ||
| Reactivity of 3MLCT(diimine) excited states | 5686 | ||
| Conclusion | 5686 | ||
| References | 5688 | ||
| Chapter 8.07: Photophysics and Photochemistry of Non-Carbonyl-Containing Coordination and Organometallic Compounds | 5693 | ||
| Introduction, Scope, and Limitations | 5693 | ||
| Electronic Structure | 5694 | ||
| Crystal Field Theory | 5694 | ||
| Ligand-Field Theory | 5696 | ||
| Molecular Orbital Theory | 5696 | ||
| Electronic Transitions and Excited States | 5699 | ||
| Absorption Bands | 5699 | ||
| MC (Ligand-Field) Bands | 5699 | ||
| CT Bands | 5701 | ||
| LC (Intra-Ligand) Bands | 5702 | ||
| Additional Considerations | 5702 | ||
| Absorption Band width and Excited-State Properties | 5703 | ||
| Excited-State Decays: Jablonski Diagram | 5704 | ||
| General Considerations on the Properties of Excited States | 5704 | ||
| Excited States and Photochemical Reactivity | 5705 | ||
| MC Excited States | 5705 | ||
| CT Excited States | 5705 | ||
| LC Excited States | 5706 | ||
| Photophysical Properties: Experimental Guidelines for Luminescence Decay of MC, CT, and LC Excited States | 5706 | ||
| Selected Examples | 5706 | ||
| Ruthenium | 5706 | ||
| General considerations | 5706 | ||
| Photophysical properties of selected ruthenium(II) compounds | 5708 | ||
| Osmium | 5709 | ||
| Copper | 5710 | ||
| General considerations | 5710 | ||
| Copper compounds: MLCT emitters | 5710 | ||
| Excited-state distortion and MLCT luminescence of Cu(I) complexes | 5711 | ||
| Luminescence of copper halide clusters | 5713 | ||
| Rhenium | 5713 | ||
| Iridium | 5714 | ||
| General considerations | 5714 | ||
| Selected classes of luminescent iridium compounds | 5714 | ||
| Platinum and Gold | 5715 | ||
| Other Topics | 5716 | ||
| Tables of Luminescence Data and Chart of Ligands Structures | 5716 | ||
| Conclusion | 5716 | ||
| Acknowledgments | 5769 | ||
| References | 5769 | ||
| Chapter 8.08: Photophysics of Lanthanoid Coordination Compounds | 5777 | ||
| Electronic Properties of Lanthanoid Ions | 5778 | ||
| The Elements | 5778 | ||
| Electronic Levels of Trivalent Ions | 5779 | ||
| Free ions | 5779 | ||
| Ligand-field effects | 5780 | ||
| Absorption Spectra | 5780 | ||
| Intraconfigurational f-f spectra | 5781 | ||
| Allowed 4f-5d Transitions | 5782 | ||
| Allowed CT Transitions | 5783 | ||
| Emission Spectra | 5784 | ||
| Basic Parameters | 5784 | ||
| Sensitization of LnIII Luminescence by Organic Ligands | 5786 | ||
| General considerations | 5786 | ||
| Theoretical modeling | 5787 | ||
| Role of the triplet state(s) | 5790 | ||
| Role of the singlet state(s) | 5792 | ||
| Influence of CT states | 5794 | ||
| Role of the Radiative Lifetime | 5796 | ||
| Quenching effect of photoinduced electron transfer in EuIII complexes | 5797 | ||
| Role of high-energy oscillators: OH vibrations | 5798 | ||
| Role of high-energy oscillators: CH vibrations and NIR luminescence | 5802 | ||
| Role of low-energy vibrations: Ln-O versus Ln-S vibrations in NIR luminescence | 5803 | ||
| Highly luminescent LnIII-containing molecules and materials | 5804 | ||
| Visible-emitting lanthanoid(III) complexes | 5804 | ||
| Sensitization of LnIII Luminescence by d-Transition-Metal Ions | 5807 | ||
| Chromium | 5807 | ||
| Manganese | 5810 | ||
| Iron | 5810 | ||
| Cobalt | 5810 | ||
| Nickel | 5810 | ||
| Copper | 5810 | ||
| Zinc | 5811 | ||
| Molybdenum, tungsten | 5811 | ||
| Rhenium | 5811 | ||
| Ruthenium, osmium | 5812 | ||
| Iridium | 5814 | ||
| Palladium, platinum | 5814 | ||
| Silver, gold | 5814 | ||
| Cadmium, mercury | 5816 | ||
| Control of LnIII Lifetime by d-Transition-Metal Ions | 5817 | ||
| Sensitization of LnIII Luminescence by Lanthanoid Ions | 5818 | ||
| Multiphotonic Excitation | 5819 | ||
| Overview of Main Applications | 5820 | ||
| Bioanalyses and Bioimaging | 5820 | ||
| Immunoassays | 5821 | ||
| Responsive probes | 5823 | ||
| Bioimaging | 5824 | ||
| Future trends | 5825 | ||
| Telecommunications | 5825 | ||
| Electroluminescent Materials: OLEDs | 5826 | ||
| Photovoltaics | 5828 | ||
| Silicon solar cells | 5828 | ||
| Dye-sensitized solar cells | 5829 | ||
| Photocatalysis | 5830 | ||
| Conclusion | 5830 | ||
| Acknowledgment | 5830 | ||
| References | 5830 | ||
| Chapter 8.09: Bond Activation and Catalysis | 5837 | ||
| Introduction | 5837 | ||
| C—H Bond Activation and Catalysis | 5838 | ||
| C—H Activation Mechanisms | 5838 | ||
| Oxidative addition | 5839 | ||
| Activation of primary versus secondary Csp3—H bonds and influence of the metal center (Rh vs. Ir) | 5839 | ||
| Activation of aromatic versus aliphatic C—H bonds | 5839 | ||
| σ-Bond metathesis | 5840 | ||
| Complex-assisted metathesis | 5841 | ||
| Oxidative addition versus sigma-bond metathesis | 5842 | ||
| 1,2-Addition | 5842 | ||
| Base-assisted C—H activation | 5844 | ||
| Selectivity of the C—H Activation | 5844 | ||
| Functionalization by Intermolecular C—H Bond Activation | 5846 | ||
| Functionalization of Csp3—H bonds by intermolecular activation | 5846 | ||
| Alkane oxidation by Shilov-related systems | 5847 | ||
| Alkane dehydrogenation | 5848 | ||
| Alkane borylation | 5849 | ||
| Alkane carbonylation | 5850 | ||
| Functionalization of unsaturated carbon atoms by intermolecular activation | 5850 | ||
| Borylation of arenes | 5850 | ||
| Reactions with carbon monoxide | 5851 | ||
| Hydroacylation | 5851 | ||
| Hydroarylation | 5851 | ||
| Arylation of alkenes | 5852 | ||
| Silylation of arenes | 5853 | ||
| Functionalization by Intramolecular C—H Bond Activation | 5853 | ||
| Functionalization of Csp3—H bonds by intramolecular activation | 5854 | ||
| Reactions with carbon monoxide | 5854 | ||
| Formation of C—C bonds from saturated hydrocarbons | 5854 | ||
| Functionalization of unsaturated carbon atoms by intramolecular activation | 5854 | ||
| Borylation | 5854 | ||
| Reactions with carbon monoxide | 5855 | ||
| Hydroacylation | 5856 | ||
| Hydroarylation | 5857 | ||
| Arylation of alkenes | 5857 | ||
| Silylation of aromatic C—H bonds | 5858 | ||
| Arene-arene coupling | 5859 | ||
| CarbonHalogen Bond Activation and Catalysis | 5860 | ||
| General Remarks about Reaction Mechanisms | 5860 | ||
| Aryl-alkenyl coupling (Heck reaction) | 5860 | ||
| Transition-metal-catalyzed cross-coupling reactions of organometallics containing B, Sn, Zn, and Mg with organochlorides | 5860 | ||
| Transition-metal-catalyzed alkynylation of organochlorides | 5860 | ||
| Transition-metal-catalyzed dechlorination of organochlorides | 5860 | ||
| Some Relevant Examples of C—Cl Bond Activation Processes | 5861 | ||
| Csp2—Cl bond activation in cross-coupling processes | 5861 | ||
| Aryl-alkenyl coupling (Heck reaction) | 5861 | ||
| Transition-metal-catalyzed cross-coupling reactions of organometallics containing B, Sn, Zn, and Mg, with organ | 5862 | ||
| Transition-metal-catalyzed alkynylation of organochlorides | 5863 | ||
| Transition-metal-catalyzed arylation of carbonyl compounds | 5863 | ||
| Transition-metal-catalyzed carbonheteroatom bond formation by cross-coupling reactions | 5863 | ||
| Csp3—Cl bond activation in cross-coupling processes | 5863 | ||
| Alkyl chlorides in Suzuki reactions | 5864 | ||
| Alkyl chlorides in Negishi reactions | 5864 | ||
| Alkyl chlorides in Kumada reactions | 5864 | ||
| Alkyl chlorides in Sonogashira reactions | 5864 | ||
| Hydrodechlorination | 5864 | ||
| Reductive hydrodechlorination | 5864 | ||
| Processes Involving Carbon—Fluorine Bond Activation | 5865 | ||
| Csp2—F bond activation in cross-coupling processes | 5865 | ||
| Aryl fluorides in Suzuki reactions | 5865 | ||
| Aryl fluorides in Kumada reactions | 5865 | ||
| Aryl fluorides in other cross-coupling reactions | 5865 | ||
| Csp3—F bond activation in cross-coupling processes | 5865 | ||
| Hydrodefluorination | 5866 | ||
| Transition-metal-catalyzed hydrodefluorination processes of aryl fluorides | 5866 | ||
| Transition-metal-catalyzed hydrodefluorination processes of alkyl fluorides | 5866 | ||
| Conclusion | 5866 | ||
| References | 5866 | ||
| Chapter 8.10: Bimetallic Approaches in Olefin Polymerization and Metathesis | 5871 | ||
| Introduction | 5871 | ||
| Bimetallic Olefin Polymerization | 5871 | ||
| Cooperativity Effects in Bimetallic Olefin Polymerization | 5872 | ||
| Early Transition Metal Catalysts | 5873 | ||
| Metallocene-based bimetallic catalysts | 5873 | ||
| Metallocenes linked by alkyl and aryl bridges | 5874 | ||
| Metallocenes linked by heteroatom bridges | 5876 | ||
| Half-metallocenes and CGCs | 5877 | ||
| Heterobimetallic metallocenes | 5878 | ||
| Nonmetallocene catalysts | 5878 | ||
| Mid- and Late Transition Metal Catalysts | 5879 | ||
| α-Diimine-type bimetallic catalysts | 5879 | ||
| Bimetallic iminopyridyl-type catalysts | 5880 | ||
| Phenoxyiminato-type catalysts | 5882 | ||
| Catalysts with miscellaneous ligations | 5884 | ||
| Early/Late Hetero- and Multimetallic Catalysts | 5885 | ||
| Bimetallic Olefin Metathesis | 5886 | ||
| Introduction | 5886 | ||
| Cooperativity Effects in Olefin Metathesis | 5887 | ||
| Bimetallic Metathesis Catalysts with Single-Centered Reactivity | 5889 | ||
| Bimetallic Metathesis Catalysts with Double-Centered Cooperative Reactivity | 5893 | ||
| Conclusion | 5893 | ||
| References | 5894 | ||
| Chapter 8.11: Catalysis of Redox Reactions | 5897 | ||
| Introduction | 5897 | ||
| Classification of ET Reactions: Outer-Sphere, Inner-Sphere, Ion Transfer, Proton Transfer, and Catalytic and Noncatalytic... | 5897 | ||
| General Theory of Multi-ET Reactions: Thermodynamics and Kinetics | 5898 | ||
| Hydrogen Evolution and Activation | 5900 | ||
| Oxygen Reduction and Oxygen Evolution - Water Splitting | 5905 | ||
| Oxygen Reduction Reaction | 5905 | ||
| Oxygen Evolution Reaction | 5908 | ||
| Reduction of CO2 | 5909 | ||
| Conclusion | 5910 | ||
| References | 5911 | ||
| Chapter 8.12: Carbon Dioxide Capture and Activation | 5913 | ||
| Introduction | 5914 | ||
| Carbon Dioxide Capture | 5914 | ||
| Current Methods of CO2 Capture | 5915 | ||
| New Directions in CO2 Capture | 5915 | ||
| Carbon Dioxide Binding and Insertion to Metal Complexes | 5917 | ||
| Structures of Metal-CO2 Complexes | 5917 | ||
| Thermodynamics and Kinetics of the Formation of M-CO2 Species | 5918 | ||
| CO2 Insertion Reactions into M-E (E=O, N, C) | 5921 | ||
| CO2/Epoxide Copolymerization | 5921 | ||
| CO2 Hydrogenation | 5922 | ||
| Reactions of M-H with CO2 | 5924 | ||
| CO2 Hydrogenation by H2 | 5924 | ||
| Electrochemical (and Chemical) Reduction of CO2 | 5925 | ||
| Metal Electrodes | 5925 | ||
| Co and Ni Macrocycles | 5926 | ||
| Ru and Os Complexes | 5927 | ||
| Re Complexes | 5928 | ||
| Pd Phosphane Complexes | 5929 | ||
| Photochemical Reduction of CO2 | 5931 | ||
| Molecular Systems | 5931 | ||
| Bimolecular systems with Ru(bpy)32+ or related complexes as a sensitizer | 5931 | ||
| Bimolecular systems with an organic photosensitizer and a metal catalyst | 5932 | ||
| Photochemical CO2 reduction by metalloporphyrins and related species | 5933 | ||
| Re(bpy)(CO)3X and related systems | 5933 | ||
| Supramolecular systems | 5934 | ||
| CO2 reduction in scCO2 or related systems (new approaches to photocatalytic CO2 reduction) | 5935 | ||
| Metal Catalysts on Semiconductors, Silicates, etc. | 5936 | ||
| Solar Thermal Conversion of CO2 into Fuel | 5938 | ||
| Conclusion | 5939 | ||
| Acknowledgments | 5940 | ||
| References | 5940 | ||
| Chapter 8.13: Water Oxidation | 5943 | ||
| Introduction | 5943 | ||
| Proton-Coupled Electron Transfer and WO Thermodynamics | 5944 | ||
| O-O Bond Formation Mechanisms | 5945 | ||
| Molecular WOCs | 5946 | ||
| Ru-Based Polynuclear WOCs | 5946 | ||
| Ru-Based Mononuclear WOCs | 5952 | ||
| Ir-Based WOCs | 5954 | ||
| First-Row Transition Metals as WOCs | 5956 | ||
| Photoelectrochemically Driven WO Catalysis and First Examples of Water-Splitting Cells | 5957 | ||
| Conclusion | 5959 | ||
| Acknowledgments | 5959 | ||
| References | 5959 | ||
| Chapter 8.14: Nitrogen Activation | 5963 | ||
| Introduction | 5963 | ||
| Theory of Dinitrogen Activation | 5964 | ||
| Inertness of N2 | 5964 | ||
| Coordination of N2 to Metal Complexes | 5964 | ||
| N2 bonding to a single metal center | 5965 | ||
| N2 bonding to two or more metal centers | 5965 | ||
| Measuring the Extent of N2 Activation | 5967 | ||
| Complexes with Coordinated Dinitrogen | 5968 | ||
| End-On Coordination of N2 | 5969 | ||
| Side-On Coordination of N2 | 5970 | ||
| Lanthanides | 5970 | ||
| Actinides | 5971 | ||
| Transition metals | 5971 | ||
| Side-On/End-On Coordination of N2 | 5972 | ||
| Uses for Activated Dinitrogen-Containing Complexes: NH3 Formation | 5972 | ||
| Early Studies | 5972 | ||
| Molybdenum Systems | 5973 | ||
| Other Metals | 5973 | ||
| Iron Complexes | 5975 | ||
| Reduced Dinitrogen Complexes | 5976 | ||
| Incorporation of Nitrogen Derived from M-N2 Complexes into Organic Molecules | 5977 | ||
| Reactions of End-On-Bonded N2 Complexes | 5979 | ||
| N―C bond formation: dinitrogen to diazenido | 5979 | ||
| N―heteroatom bond formation | 5981 | ||
| N―Si, N―Ge bond formation | 5981 | ||
| N―B bond formation | 5982 | ||
| Alkylation of the coordinating nitrogen | 5982 | ||
| Reactions of diazenido complexes | 5982 | ||
| Hydrazido complexes from dinitrogen complexes | 5982 | ||
| Si functionalization | 5983 | ||
| N―C Bond Formation from Hydrazido Complexes | 5983 | ||
| Hydrazido condensations | 5983 | ||
| Hydrazido to amino | 5984 | ||
| Direct Cleavage of the N≡N Bond: Nitride Complexes | 5984 | ||
| N―C Bond Formations Utilizing Multiple Metal Centers | 5985 | ||
| Biological Activation of N2: N2 Reduction and Nitrogenase Models and Mimics | 5987 | ||
| Nitrogenase | 5987 | ||
| Cubane Cluster Nitrogenase Models | 5987 | ||
| Vanadium-Nitrogenase Models | 5988 | ||
| Conclusion | 5988 | ||
| References | 5988 | ||
| Chapter 8.15: Solar Fuels: Approaches to Catalytic Hydrogen Evolution | 5991 | ||
| Solar Fuels | 5991 | ||
| Background | 5991 | ||
| Devices for Artificial Photosynthesis | 5991 | ||
| Catalytic H2 Production | 5992 | ||
| Electrocatalysis | 5992 | ||
| Biomimetic Systems | 5992 | ||
| Molecular Hydrogen-Evolving Complexes | 5993 | ||
| Cobaloximes | 5995 | ||
| Electrochemical systems | 5995 | ||
| Photochemical systems | 5997 | ||
| Reaction pathways | 5998 | ||
| Mechanistic analysis | 5999 | ||
| Mechanistic insights from electrochemical experiments | 5999 | ||
| Mechanistic insights from bulk photochemical experiments | 6000 | ||
| Mechanistic insights from time-resolved spectroscopy | 6000 | ||
| Conclusion | 6002 | ||
| Acknowledgments | 6002 | ||
| References | 6002 | ||
| Chapter 8.16: Organic Photovoltaics and Dye-Sensitized Solar Cells | 6005 | ||
| Background | 6006 | ||
| Parameters of Solar Cells | 6006 | ||
| Organic Photovoltaics | 6007 | ||
| Construction and Work Principle | 6007 | ||
| Porphyrins | 6007 | ||
| Phthalocyanines | 6011 | ||
| Pt Polymers and Oligomers | 6014 | ||
| Other Coordination and Organometallic Compounds | 6016 | ||
| Dye-Sensitized Solar Cells | 6017 | ||
| Construction and Work Principle | 6017 | ||
| Photosensitizers | 6019 | ||
| Porphyrins and corroles | 6020 | ||
| Phthalocyanines | 6023 | ||
| Ru complexes | 6026 | ||
| Pt complexes | 6030 | ||
| Cu complexes | 6032 | ||
| Other complexes | 6032 | ||
| Redox Couples | 6033 | ||
| Fe complexes | 6034 | ||
| Cu complexes | 6036 | ||
| Ni complexes | 6037 | ||
| Co complexes | 6038 | ||
| Conclusion | 6039 | ||
| References | 6039 | ||
| Chapter 8.17: Luminescent Coordination and Organometallic Complexes for OLEDs | 6045 | ||
| Introduction | 6045 | ||
| Phosphorescent Third row Transition Metal Complexes | 6045 | ||
| Rhenium(I) Complexes | 6046 | ||
| Osmium(II) Complexes | 6048 | ||
| Osmium complexes with neutral diimine ligand(s) | 6048 | ||
| Osmium complexes with anionic ligand(s) | 6048 | ||
| Iridium(III) Complexes | 6050 | ||
| Iridium(III) complexes with bidentate ligands | 6050 | ||
| Homoleptic and heteroleptic iridium(III) complexes with bidenate ligands | 6050 | ||
| Iridium(III) complexes as blue emitter | 6051 | ||
| Iridium(III) complexes as red emitters | 6052 | ||
| Iridium(III) complexes as near-infrared emitters | 6052 | ||
| Iridium(III) complexes for WOLED | 6053 | ||
| Iridium(III) complexes with N,N-heteroaromatic ligands | 6053 | ||
| Iridium(III) complexes with multifunctional ligands | 6054 | ||
| Stability and isomerism of homoleptic and heteroleptic Iridium(III) complexes | 6055 | ||
| Iridium(III) complexes for solution-processed OLED | 6056 | ||
| Iridium(III) complexes with tridentate ligands | 6060 | ||
| Platinum(II) Complexes | 6061 | ||
| Platinum(II) porphyrins | 6061 | ||
| Platinum(II) complexes bearing bidentate ligands | 6062 | ||
| Platinum(II) complexes having bidentate (N^C)- ligands | 6062 | ||
| Platinum(II) complexes with bidentate (N^N*)- ligands | 6065 | ||
| Platinum(II) complexes with tridentate ligands | 6065 | ||
| Platinum(II) complexes with tridentate (C^N^N)- ligands | 6065 | ||
| Platinum(II) complexes with tridentate (N^C^N)- ligands | 6067 | ||
| Platinum(II) complexes with tridentate (Bz^C^Bz)- ligands | 6067 | ||
| Platinum(II) complexes with tridentate (O^N^N)- ligands | 6068 | ||
| Strategy for developing emissive tridentate platinum(II) complexes | 6068 | ||
| Platinum(II) complexes with tetradentate ligands | 6069 | ||
| Platinum(II) complexes with (O^N^N^O)2- ligands | 6069 | ||
| Platinum(II) complexes with Schiff-base ligands | 6069 | ||
| Platinum(II) complexes with tetradentate (N*^N^N^N*)2- ligands | 6071 | ||
| Platinum(II) complexes with tetradentate (O^C*^C*^O)2- ligands | 6072 | ||
| Platinum(II) complexes with tetradentate (N^C^C^N)2- ligands | 6072 | ||
| Platinum(II) complexes for solution-processed OLEDs | 6073 | ||
| Emission color tuning of phosphorescent platinum(II) complexes | 6074 | ||
| Gold(I) and Gold(III) Complexes | 6076 | ||
| Other Metal Complexes Used in OLED | 6078 | ||
| Aluminum(III) Complexes | 6078 | ||
| Ruthenium(II) Complexes | 6080 | ||
| Copper(I) Complexes | 6080 | ||
| Zn(II) Complexes | 6081 | ||
| Conclusion | 6088 | ||
| References | 6090 | ||
| Chapter 8.18: Chemosensing and Diagnostics | 6095 | ||
| Introduction | 6096 | ||
| pH Sensors | 6096 | ||
| Carboxyl Complexes | 6096 | ||
| Aromatic Hydroxyl Complexes | 6096 | ||
| Amine Complexes | 6097 | ||
| Pyridine-Pendant Complexes | 6099 | ||
| Complexes with Multiple Protonation Sites | 6100 | ||
| Proton-Induced Changes in Emission Wavelength | 6101 | ||
| Metal-Cation Sensors | 6102 | ||
| Crown-Ether Complexes | 6102 | ||
| Pyridine-Pendant Complexes | 6108 | ||
| Mercury-Sulfur Interaction | 6110 | ||
| Other Systems | 6111 | ||
| Anion Sensors | 6112 | ||
| Fluoride Sensors Based on Hydrogen-Fluoride Interaction | 6112 | ||
| Fluoride Sensors Based on Triarylboron-Fluoride Interaction | 6113 | ||
| Other Anion Sensors Based on Hydrogen-Bonding Interaction | 6116 | ||
| Other Systems | 6118 | ||
| Small-Molecule Sensors | 6121 | ||
| Oxygen Sensors | 6121 | ||
| Organic Vapor Sensors | 6123 | ||
| Sugar Sensors | 6129 | ||
| Nucleotide Sensors | 6130 | ||
| Amino Acid Sensors | 6130 | ||
| Nucleic Acid Sensors | 6132 | ||
| Electrostatic Interaction | 6132 | ||
| Metallointercalators | 6132 | ||
| Groove Binders | 6137 | ||
| Dinuclear Metal Complexes | 6138 | ||
| RNA Sensors | 6139 | ||
| Protein Sensors | 6140 | ||
| Binding to Amino Acids | 6140 | ||
| Nonspecific Hydrophobic Interaction | 6140 | ||
| Specific Protein-Substrate Interaction | 6141 | ||
| Dual Emissive Probes | 6147 | ||
| Label-Free Detection | 6148 | ||
| Cellular Sensors | 6149 | ||
| Lipophilicity on Cellular Uptake | 6150 | ||
| Formal Charge on Cellular Uptake | 6155 | ||
| Receptor-Mediated Uptake | 6155 | ||
| Cytotoxicity | 6156 | ||
| Membrane Dyes | 6156 | ||
| Cytoplasm Dyes | 6157 | ||
| Organelle-Specific Dyes | 6158 | ||
| Nuclear Uptake | 6159 | ||
| Intracellular Sensing | 6160 | ||
| Conclusion | 6166 | ||
| Acknowledgments | 6166 | ||
| References | 6166 | ||
| Chapter 8.19: Molecular Imaging: Chemistry and Applications | 6171 | ||
| Molecular Imaging: A Brief Introduction | 6171 | ||
| Fluorescence Sensing and Imaging of Biological Inorganic Species | 6172 | ||
| Fluorescence and Fluorescence Imaging2 | 6172 | ||
| Single-Photon and Two-Photon Fluorescence Imaging | 6173 | ||
| Fluorescence Lifetime Imaging Microscopy | 6173 | ||
| Fluorescent Probes and Fluorescence Imaging | 6174 | ||
| Small molecular probes | 6174 | ||
| Macromolecule-based probes | 6175 | ||
| Inorganic nanomaterial-based fluorophores | 6175 | ||
| Quantum dots | 6175 | ||
| LnIII-doped upconversion luminescent nanoparticles | 6176 | ||
| Surface modification of UCLs and QDs for probe construction | 6176 | ||
| Intensity-based fluorescent probes | 6176 | ||
| Fluorescent probes displaying analyte-induced emission enhancement (turn-on probes) | 6177 | ||
| Fluorescent probes displaying analyte-induced emission/excitation shift (ratiometric probes) | 6177 | ||
| FRET-based ratiometric probes | 6177 | ||
| PCT-based ratiometric probes | 6177 | ||
| Fluorophore coplanation-based ratiometric probes | 6178 | ||
| Ratiometric probes based on excimer formation | 6178 | ||
| Probes for FLIM | 6178 | ||
| Probes for Biological Inorganic Species and Related Imaging | 6179 | ||
| Probes for Ca2 | 6180 | ||
| Probes for Mg2 | 6181 | ||
| Probes for Na+ and K | 6181 | ||
| Probes for pH | 6183 | ||
| Probes for Zn2 | 6184 | ||
| Probes for other transition metal cations | 6188 | ||
| Probes for Cl- and phosphate anions | 6190 | ||
| Probes for NO and H2S | 6194 | ||
| Probes for ROS (reactive oxygen species) | 6197 | ||
| MRI and Gd3+-Based Contrast Agents (GBCAs) | 6201 | ||
| GBCAs for T1-Weighted MRI | 6203 | ||
| Optimization of GBCA structure | 6203 | ||
| Modulation of the number of bound inner-sphere water molecules | 6204 | ||
| Optimization of residence time | 6204 | ||
| Optimization of rotational tumbling time | 6205 | ||
| Responsive GBCAs (Gd3+-Based MRI Probes) | 6206 | ||
| Analyte altering the number of inner-sphere bound water molecules (q) | 6206 | ||
| Analyte altering the rotational tumbling time (tauR) | 6206 | ||
| PET/SPECT and the Metal Complex-Based Radiotracers | 6207 | ||
| BFCs for 64Cu and 99mTc | 6208 | ||
| 64Cu chelating BFCs and in vivo stability of related complexes for PET | 6208 | ||
| 99mTc chelating BFCs for SPECT | 6210 | ||
| Bioconjugation of BFCs for Targeting Imaging | 6210 | ||
| Multimodal Imaging Agents | 6212 | ||
| Conclusion | 6214 | ||
| References | 6215 | ||
| Chapter 8.20: Nonlinear Optical Properties of Coordination and Organometallic Complexes | 6219 | ||
| Introduction | 6220 | ||
| Theory | 6220 | ||
| Measurement Techniques | 6221 | ||
| Determination of the quadratic NLO properties of molecules | 6221 | ||
| Determination of the cubic NLO and optical limiting properties of molecules | 6223 | ||
| Units | 6224 | ||
| Second-Order Nonlinearities | 6224 | ||
| Complexes of Pyridyl, Polypyridyl, and Related Ligands | 6224 | ||
| Complexes of Porphyrins and Related Ligands | 6231 | ||
| Complexes of Other N- and/or O-Donor Ligands | 6234 | ||
| Metal Alkynyl Complexes | 6237 | ||
| Metallocenyl Complexes | 6238 | ||
| Third-Order Nonlinearities | 6238 | ||
| Complexes of Pyridyl, Polypyridyl, and Related Ligands | 6238 | ||
| Complexes of Porphyrins and Related Ligands | 6241 | ||
| Complexes of Other N- and/or O-Donor Ligands | 6251 | ||
| Metal Alkynyl Complexes | 6253 | ||
| Cluster Complexes | 6257 | ||
| Other Complexes | 6257 | ||
| Conclusion | 6265 | ||
| References | 6265 | ||
| Chapter 8.21: Metallomesogens | 6275 | ||
| Preamble | 6276 | ||
| General Introduction | 6276 | ||
| Thermotropic Liquid Crystals | 6276 | ||
| Calamitic Mesogens | 6277 | ||
| Mesophases of Calamitic Mesogens | 6277 | ||
| The nematic phase | 6277 | ||
| The chiral nematic phase | 6277 | ||
| The true smectic phases | 6278 | ||
| Discotic Mesogens | 6279 | ||
| Mesophases of Disk-Like Mesogens | 6279 | ||
| Polycatenar Liquid Crystals | 6280 | ||
| Lyotropic Liquid Crystals | 6280 | ||
| Physical Properties and Mesophase Characterization | 6282 | ||
| Physical Properties | 6282 | ||
| Mesophase Characterization | 6283 | ||
| General Overview of Metallomesogens Types | 6284 | ||
| Metal Carboxylate Mesogens | 6284 | ||
| Carboxylates of monovalent metals | 6284 | ||
| Carboxylates of divalent metals | 6284 | ||
| Tetra(carboxylato)dimetal mesogens | 6284 | ||
| Macrocyclic Metallomesogens | 6285 | ||
| Metallophthalocyanine mesogens | 6285 | ||
| Metalloporphyrin mesogens | 6288 | ||
| Other macrocyclic metallomesogens | 6291 | ||
| Complexes of Mono- and Bi-Dentate Ligands | 6292 | ||
| β-Diketonato metal complexes | 6292 | ||
| Other O,O-donor ligands | 6295 | ||
| S,S-Donor ligands | 6296 | ||
| Enaminoketones | 6297 | ||
| Salicylaldimine derivatives | 6298 | ||
| Other N,O-donor ligands | 6300 | ||
| Pyrazole-based ligands | 6301 | ||
| Pyridines, bipyridines, and related ligands | 6302 | ||
| Other N,N-donor ligands | 6305 | ||
| Nitriles, isonitriles, and acetylides | 6306 | ||
| Miscellaneous organometallic systems | 6309 | ||
| Ferrocene-Containing Metallomesogens | 6310 | ||
| Liquid-Crystalline Metallodendrimers | 6312 | ||
| Miscellaneous | 6314 | ||
| Ortho-Metallated Metallomesogens | 6315 | ||
| Ortho-Metallated Palladium(II) and Platinum(II) Complexes | 6315 | ||
| Ortho-metallated azo, azoxy, and azine complexes | 6316 | ||
| Ortho-Metallated imine complexes | 6319 | ||
| Ortho-metallated pyrimidine, pyridazine, and pyridine complexes | 6324 | ||
| Other ortho-metallated complexes | 6328 | ||
| Octahedral Ortho-Metallated Complexes | 6330 | ||
| Lanthanide-Containing Liquid Crystals and Magnetic Responses of Metallomesogens | 6331 | ||
| Lanthanide-Containing Liquid Crystals | 6332 | ||
| Macrocycles | 6332 | ||
| Salicylaldimines | 6334 | ||
| N-Donor chelating ligands | 6336 | ||
| Magnetic Properties of Metallomesogens | 6337 | ||
| Magnetic alignment and magnetic anisotropy | 6337 | ||
| Single-molecule magnets | 6338 | ||
| Spin-crossover compounds | 6339 | ||
| Magnetic susceptibility of mesogenic carboxylates and polymeric acetylides | 6341 | ||
| Conclusion | 6342 | ||
| Acknowledgment | 6342 | ||
| References | 6342 | ||
| Chapter 8.22: Electrochromic and Photochromic Properties | 6357 | ||
| General Introduction | 6358 | ||
| Electrochromic Transition Metal Complexes and Organometallics | 6358 | ||
| Introduction | 6358 | ||
| Electrochromism with Linkage Isomerization | 6358 | ||
| Ruthenium sulfoxide and polypyridyl complexes | 6358 | ||
| Copper pyridylpyrimidine complexes | 6359 | ||
| Electrochromism with Intramolecular Ligand Exchange Reactions | 6360 | ||
| Catenanic copper complexes | 6360 | ||
| Rotaxanic copper complexes | 6360 | ||
| Electrochromism without Large Structural Changes | 6360 | ||
| Redox-active metal complexes and organometallics | 6360 | ||
| Redox-regulated NLO properties | 6362 | ||
| Prussian Blue | 6363 | ||
| Photochromic Transition Metal Complexes and Organometallics | 6365 | ||
| Introduction | 6365 | ||
| Photochromism with Linkage Isomerization | 6366 | ||
| Nitrito complexes and organometallics | 6366 | ||
| Nitrosyl complexes and organometallics | 6366 | ||
| Ruthenium sulfoxide complexes | 6366 | ||
| Rhodium dithionite cluster complexes | 6367 | ||
| Linkage isomerization with organic ambidentate ligands | 6367 | ||
| Other linkage isomerization complexes | 6368 | ||
| Photochromism with Intramolecular Ligand Exchange Reactions | 6368 | ||
| Rotaxanic and catenanic copper complexes | 6368 | ||
| Catenanic ruthenium complexes | 6369 | ||
| Photochromism with Bond Reorganization | 6370 | ||
| Fulvalene-containing organometallics | 6370 | ||
| Haptotropic rearrangement | 6370 | ||
| Photochromism without Large Structural Changes | 6370 | ||
| Light-induced excited spin state trapping (LIESST) | 6370 | ||
| Light-induced CT-induced spin transition | 6372 | ||
| Interplay among Transition Metal Complexes, Organometallics, and Organic Photochromics | 6376 | ||
| Introduction | 6376 | ||
| Organic Photochromics | 6378 | ||
| Control over the Photo-, Electro-, and Magneto-Properties of Transition Metal Complexes and Organometallics via Photois... | 6378 | ||
| ON/OFF switching of luminescence | 6378 | ||
| Modulation of electronic communication in MV states | 6379 | ||
| Control over the magnetism | 6380 | ||
| Regulation of the coordination environment around a metal center | 6381 | ||
| NLO switching | 6385 | ||
| Control over the Isomerization Behavior of Organic Photochromics by Transition Metal Complexes and Organometallics | 6386 | ||
| Electrochromism triggered by redox switching of metal moieties | 6386 | ||
| ON/OFF switching of photochromism via redox switching of the metal centers | 6386 | ||
| Modulation of the photoresponsive wavelength | 6389 | ||
| NIR photochromism | 6391 | ||
| Mutual Controls | 6393 | ||
| Multiphotochromic Systems | 6396 | ||
| Other Types of Conjugates | 6397 | ||
| Conclusion | 6399 | ||
| References | 6400 | ||
| Chapter 8.23: Molecular Switching, Logics, and Memories | 6407 | ||
| Molecular Switching | 6407 | ||
| Light-Induced Molecular Switching | 6408 | ||
| Metal ion-based molecular switching | 6408 | ||
| Switching molecules through different redox states | 6409 | ||
| Switching of photobistable systems | 6409 | ||
| Metal complexes with azobenzene groups | 6409 | ||
| Metal complexes with diarylethene groups | 6422 | ||
| Stilbene | 6422 | ||
| Cyclic diarylethenes | 6424 | ||
| Metal complexes with spirocyclic groups | 6440 | ||
| Spiropyran | 6440 | ||
| Spirooxazine | 6446 | ||
| Metal complexes with rhodamine and other groups | 6447 | ||
| Switching by complexation/decomplexation | 6449 | ||
| Molecular Logics | 6451 | ||
| Single Input | 6451 | ||
| Two Inputs and One Output: AND, OR, INH, NOR, and XNOR Logic Gates | 6451 | ||
| AND logic gate | 6452 | ||
| OR logic gate | 6452 | ||
| XOR logic gate | 6453 | ||
| INH logic gate | 6454 | ||
| NOR logic gate | 6454 | ||
| XNOR logic gate | 6455 | ||
| Interchangeable logic gates | 6455 | ||
| Two Inputs, Two Outputs; Half-Adder, Half-Subtractor | 6456 | ||
| Other systems with dual-inputs, dual-outputs | 6459 | ||
| Three Inputs, Full-Adder and Full-Subtractor | 6460 | ||
| Other Systems | 6461 | ||
| Encoder-decoder | 6461 | ||
| Three Inputs and a Single Output | 6461 | ||
| Other Examples | 6463 | ||
| Reversible molecular logic: Feynman gate | 6463 | ||
| Set-reset logic | 6464 | ||
| Monolayer devices for Boolean logic gates | 6465 | ||
| Monolayers deposited in a conducting surface | 6466 | ||
| Chemical Communications Between Molecular Switches | 6467 | ||
| Quantum-Dot Cellular Automata | 6470 | ||
| Memories | 6471 | ||
| Keypad Lock | 6471 | ||
| Conclusion | 6471 | ||
| References | 6472 | ||
| e9780080965291v9 | 6476 | ||
| Front Cover | 6476 | ||
| Volume 9: Theory and Methods | 6479 | ||
| Copyright | 6480 | ||
| Editorial Board | 6481 | ||
| Contributors | 6483 | ||
| Contents | 6497 | ||
| Preface | 6511 | ||
| Volume Editor´s Introduction | 6513 | ||
| Methodology | 6519 | ||
| Chapter 9.01: Theoretical Toolkits for Inorganic and Bioinorganic Complexes: Their Applications and Insights | 6519 | ||
| General Introduction | 6520 | ||
| Electronic Structure Methods | 6523 | ||
| Density Functional Theory | 6523 | ||
| Local density approximation | 6527 | ||
| General gradient approximation | 6527 | ||
| Meta-GGA-based functionals | 6528 | ||
| Hybrid DFT | 6528 | ||
| Double-hybrid DFT | 6529 | ||
| Improved functionals up the Jacob's ladder | 6529 | ||
| Orbitals in DFT: yes or no? | 6529 | ||
| Special Considerations in Applications of DFT | 6529 | ||
| Which functional should be used? | 6529 | ||
| Dispersion correction | 6530 | ||
| Symmetry-broken solution in DFT | 6531 | ||
| Self-interaction errors | 6534 | ||
| Orbital types in DFT | 6534 | ||
| Ab Initio WFT Methods | 6536 | ||
| SR methods | 6537 | ||
| MPn methods | 6537 | ||
| Spin-component-scaled MP2 | 6539 | ||
| CC methods | 6539 | ||
| Practical considerations in CC applications | 6540 | ||
| MR methods | 6542 | ||
| Complete active space SCF and restricted active space SCF | 6542 | ||
| MR second-order perturbation | 6543 | ||
| Multireference CI | 6543 | ||
| General considerations in applications of WFT methods | 6544 | ||
| Basis sets in WFT methods | 6544 | ||
| Explicit correlation local methods | 6545 | ||
| Getting more meaningful correlation | 6545 | ||
| Notes on Computational Methods for Molecular Spectroscopy | 6546 | ||
| Concluding Remarks on Electronic Structure Methods for TM and Bioinorganic Complexes | 6546 | ||
| Relativistic Effects in Computational Quantum Chemistry | 6547 | ||
| All-Electron Relativistic Calculations | 6547 | ||
| Zero order of regular approximation and infinite-order regular approximation models | 6549 | ||
| Relativistic Calculations with Effective Core Potentials | 6550 | ||
| Sources of effective core potentials | 6550 | ||
| Reliability and tips for relativistic calculations in WFT and DFT | 6550 | ||
| Some Applications of Relativistic Calculations | 6550 | ||
| Quantum Mechanical/Molecular Mechanical Methods | 6552 | ||
| Methodological Issues in QM/MM Studies | 6552 | ||
| QM/MM partitioning | 6552 | ||
| QM methods | 6553 | ||
| MM methods | 6553 | ||
| Subtractive versus additive QM/MM schemes | 6553 | ||
| Electrostatic QM/MM interactions | 6554 | ||
| Boundary treatments | 6554 | ||
| QM/MM geometry optimization | 6554 | ||
| QM/MM MD and free energy calculations | 6554 | ||
| QM/MM energy versus free energy calculations | 6554 | ||
| Practical Issues in QM/MM Studies | 6555 | ||
| QM/MM software | 6555 | ||
| QM/MM setup | 6555 | ||
| Accuracy of QM/MM results | 6555 | ||
| QM/MM geometry optimization | 6555 | ||
| Extracting insights from QM/MM calculations | 6556 | ||
| Summary | 6556 | ||
| Valence Bond Methods in Inorganic/Bioinorganic/Organometallic Chemistry | 6556 | ||
| VB Modeling of Chemical Reactivity | 6556 | ||
| Deciphering reactivity patterns of cytochrome P450 | 6557 | ||
| Bridges between the languages of bioinorganic chemistry and VB theory | 6558 | ||
| Application of the VB diagram to reactivity patterns of cytochrome P450 | 6559 | ||
| Alkane hydroxylation | 6559 | ||
| Thioether sulfoxidation | 6560 | ||
| Reactivity patterns predicted by the VB diagram model | 6561 | ||
| H-abstraction patterns in alkane hydroxylation | 6561 | ||
| Reactivity patterns in thioether sulfoxidation | 6562 | ||
| Patterns in aromatic epoxidation/hydroxylation | 6562 | ||
| The Bell-Evans-Polanyi Principle | 6563 | ||
| VB Reading of Complex Wave Functions | 6565 | ||
| VB reading of the CASSCF wave function for oxy-Mb | 6566 | ||
| VB reading of the CASSCF wave function for {Fe-NO}7 complexes | 6568 | ||
| Summary of VB applications to problems in bioinorganic chemistry | 6569 | ||
| Conclusion | 6569 | ||
| Appendix 1 | 6570 | ||
| References | 6571 | ||
| Relevant Websites | 6575 | ||
| Chapter 9.02: Computational Methods for Solids | 6577 | ||
| Part I: Foundations | 6577 | ||
| Moving to the Solid State | 6577 | ||
| Bloch's Theorem | 6578 | ||
| k Vectors and Reciprocal Space | 6579 | ||
| Band Structures: 1D, 2D, and 3D | 6580 | ||
| Two Kinds of Basis Sets | 6582 | ||
| Part II: Simplifications | 6583 | ||
| Exchange and Correlation | 6583 | ||
| Exchange-Correlation Functionals for DFT | 6585 | ||
| Cellular and Linearized Methods | 6586 | ||
| Pseudopotentials and Beyond | 6588 | ||
| Order-N Methods | 6588 | ||
| Structure Optimization | 6589 | ||
| Molecular Dynamics | 6590 | ||
| The Solid-State Chemist's Theoretical Toolkit | 6591 | ||
| Part III: Applications | 6592 | ||
| Back into Real Space: Densities of States | 6592 | ||
| Where Are the Electrons? | 6595 | ||
| Visual Bonding Indicators | 6596 | ||
| Quantum Thermochemistry | 6599 | ||
| Solid-State Nuclear Magnetic Resonance | 6601 | ||
| Strongly Correlated Materials: Pushing the Borders of DFT | 6601 | ||
| Supercomputing | 6602 | ||
| Conclusion | 6603 | ||
| Computational Details | 6603 | ||
| Acknowledgments | 6603 | ||
| References | 6603 | ||
| Bonding and Electronic Structure | 6607 | ||
| Chapter 9.03: Gas Phase Structure of Small Molecules | 6607 | ||
| Introduction | 6607 | ||
| Variations of the GED Experiment to Determine Gaseous Structure | 6608 | ||
| Traditional GED | 6608 | ||
| Ultrafast Electron Diffraction | 6612 | ||
| Combining Experimental Structural Methods | 6613 | ||
| Combined Analyses of Data Obtained by Electron Diffraction, Rotational Spectroscopy, and Liquid-Crystal NMR Spectro | 6613 | ||
| Electron Diffraction and Mass Spectrometric Measurements | 6614 | ||
| Use of Computational Methods in Structure Determination | 6615 | ||
| Molecular Orbital Constrained Electron Diffraction | 6615 | ||
| Structure Analysis Restrained by Ab Initio Calculations for Electron Diffraction | 6615 | ||
| Dynamic Interaction of Theory and Experiment and Structure Enhancement Methods for Theory and Experiment | 6617 | ||
| A Quick Tour of the Periodic Table | 6617 | ||
| Compounds Containing s-Block Elements | 6617 | ||
| Compounds Containing p-Block Elements | 6618 | ||
| Compounds Containing d-Block and f-Block Elements | 6619 | ||
| Conclusion | 6621 | ||
| References | 6621 | ||
| Relevant Websites | 6625 | ||
| Chapter 9.04: Hyperbonding and Hypercoordination in Main-Group Chemistry | 6627 | ||
| Introduction | 6627 | ||
| Nature of Hypervalent Bonding | 6629 | ||
| Carbon and Its Subgroup | 6632 | ||
| Organopnictogen Compounds | 6635 | ||
| Organochalcogen Compounds | 6639 | ||
| Hypercoordination in Main-Group Chemistry | 6640 | ||
| Hypercoordination of Carbon in the Flat Polycyclic Systems | 6641 | ||
| Hypercoordination of Boron and Nitrogen in the Flat Polycyclic Systems | 6642 | ||
| Hypercoordinate Main-Group Centers in Three-Dimensional Molecular Structures | 6643 | ||
| Conclusion | 6648 | ||
| Acknowledgments | 6648 | ||
| References | 6648 | ||
| Chapter 9.05: Molecular Structure of Solvates and Coordination Complexes in Solution as Determined with EXAFS and XANES | 6651 | ||
| Foreword | 6651 | ||
| XASs: EXAFS and XANES | 6652 | ||
| Theory | 6652 | ||
| Experimental Requirements | 6655 | ||
| Source | 6655 | ||
| Optics | 6655 | ||
| Detection systems | 6656 | ||
| The special case of solutions | 6656 | ||
| Data Analysis | 6657 | ||
| EXAFS | 6657 | ||
| XANES | 6658 | ||
| Combination with MD | 6658 | ||
| QM computations | 6659 | ||
| Structure of Metal Aqua Ions | 6659 | ||
| Octahedral Complexes: Cr(III) and Zn(II) | 6660 | ||
| Octahedral Complexes: Special Cases of Rh(III) and Ir(III) | 6661 | ||
| Square-Planar Pt(II) Complexes | 6663 | ||
| Nonsymmetric Structures: Y(III) and Cf(III) | 6663 | ||
| The Special Case of Cu(II) | 6666 | ||
| Structure of Other Complexes | 6667 | ||
| Chloride Complexes of Cr(III) and Pt(II) | 6668 | ||
| Cyanide Complexes | 6668 | ||
| Cu(II) Complexes with N-Ligands | 6670 | ||
| Oxaliplatin, a cis-Platin Family Drug | 6672 | ||
| Solvation Structure of Bromide Anions | 6673 | ||
| Bromide Hydration Structure | 6674 | ||
| Bromide Solvation Structure in Acetonitrile Solution | 6675 | ||
| Conclusion | 6675 | ||
| Acknowledgments | 6675 | ||
| References | 6675 | ||
| Relevant Website | 6625 | ||
| Chapter 9.06: Structural Aspects of Light-Excited States | 6679 | ||
| Excited State Structures | 6680 | ||
| Introduction | 6680 | ||
| Probing the Structure of Excited State | 6681 | ||
| Introduction to Diffraction and Scattering | 6681 | ||
| Diffraction by a perfect crystal | 6681 | ||
| Coexistence of two molecular states | 6682 | ||
| Coexistence of ground and excited phases | 6682 | ||
| Symmetry breaking | 6683 | ||
| Electron density analysis | 6684 | ||
| Local order and diffuse scattering | 6684 | ||
| Time-Resolved x-Ray Scattering | 6684 | ||
| 100 picosecond diffraction at synchrotron sources | 6686 | ||
| 100 femtosecond slicing at synchrotron sources | 6686 | ||
| 100 femtosecond plasma x-ray sources | 6686 | ||
| X-FEL, the new generation of x-ray source | 6687 | ||
| Scattering by Molecules in Solution | 6687 | ||
| Other Time-Resolved Structural Techniques | 6688 | ||
| x-Ray absorption spectroscopy | 6688 | ||
| Electron diffraction | 6688 | ||
| Photocrystallography of Long-Lived Excited States | 6689 | ||
| Structural Investigation of Photomagnetic Systems | 6689 | ||
| Spin-state switching: intramolecular reorganization | 6689 | ||
| Light-induced broken symmetry versus spin-state switching | 6689 | ||
| System with several excited states | 6690 | ||
| Electron density analysis | 6690 | ||
| Photomagnetic switching of heterometallic complexes | 6691 | ||
| Phase nucleation processes | 6691 | ||
| Photochemistry in Crystals | 6692 | ||
| Photoinduced linkage isomerization | 6692 | ||
| cis-trans Photo-isomerization and applications | 6693 | ||
| Dynamical Structural Science | 6694 | ||
| Coherent Atomic Motion | 6694 | ||
| Dynamical Processes of SC Materials | 6695 | ||
| x-Ray spectroscopy study: molecules in solution | 6695 | ||
| Picosecond x-ray diffraction study: transformation in crystal | 6696 | ||
| Photoinduced Ferroelectric Order | 6696 | ||
| Broken symmetry | 6696 | ||
| The dimerized photoinduced phase | 6697 | ||
| Laue Techniques Based On the Ratio Method | 6697 | ||
| Method | 6697 | ||
| Study of a dinuclear complex | 6698 | ||
| Diffuse Scattering Probing Local Nonequilibrium Phenomena | 6698 | ||
| Cooperative 1D electron transfer | 6698 | ||
| Imaging of nonequilibrium phonons | 6699 | ||
| Dynamics of Molecules in Solution | 6699 | ||
| Photodissociation in solution | 6699 | ||
| Bio-macromolecules in solution | 6700 | ||
| Conclusion | 6701 | ||
| Acknowledgments | 6701 | ||
| References | 6701 | ||
| Relevant Website | 6703 | ||
| Chapter 9.07: Electron Density Analysis | 6705 | ||
| Introduction | 6706 | ||
| Quantum Mechanical Background | 6707 | ||
| Density of Probability Distribution Functions | 6708 | ||
| Important Properties of the Electron Density | 6708 | ||
| The Source Function | 6709 | ||
| Density of Property and Related Local Functions | 6709 | ||
| Properties of the Pair Functions and Fermi Hole-Related Functions | 6710 | ||
| The Electron Localization Function (ELF) | 6710 | ||
| The Electron-Pair Localization Functions | 6711 | ||
| Determination of Electron Density and ELF | 6712 | ||
| Experimental Determination of Electron Density and One-Particle Density Matrices in Position and Momentum Space | 6712 | ||
| General remarks on available techniques and obtainable properties | 6712 | ||
| Relationships with experimental outcomes | 6712 | ||
| Additional detail on obtaining a charge density from x-ray diffraction data33,36 | 6713 | ||
| Electron Densities from Quantum Chemical Calculation | 6714 | ||
| Determination of ELF | 6715 | ||
| Methods of Analysis | 6716 | ||
| Intuitive Qualitative Interpretations | 6716 | ||
| Deformation densities | 6716 | ||
| Qualitative ELF | 6716 | ||
| Charge Density and Space Partitioning | 6716 | ||
| Sketch of the topological analysis of dynamical systems | 6718 | ||
| Statistical population analysis for nonoverlapping partition | 6719 | ||
| The Quantum Theory of Atoms in Molecules | 6720 | ||
| The atomic basin | 6720 | ||
| The bond path and the definition of the molecular structure | 6721 | ||
| The QTAIM population analysis | 6722 | ||
| Energy partitioning in the QTAIM framework | 6723 | ||
| The QTAIM classification of chemical interactions | 6724 | ||
| van der Waals interaction: Kr2 | 6725 | ||
| Hydrogen bonds | 6725 | ||
| Ionic and donor-acceptor bonds | 6726 | ||
| Metalmetal bonds | 6726 | ||
| Three-electron bond | 6727 | ||
| Charge—shift bond | 6727 | ||
| Shared interaction and polar bonds | 6727 | ||
| Aromaticity | 6728 | ||
| The Laplacian of the electron density | 6729 | ||
| ELF Interpretations | 6729 | ||
| The ELF basins and the synaptic order | 6729 | ||
| Hierarchy of the ELF basins | 6730 | ||
| The ELF population analysis | 6731 | ||
| The ELF classification of chemical interactions | 6733 | ||
| van der Waals interaction: Kr2 | 6733 | ||
| Hydrogen bonds | 6733 | ||
| Ionic bonds | 6734 | ||
| Metal—metal bonds | 6734 | ||
| Three-electron bonds | 6734 | ||
| Charge—shift bonds | 6735 | ||
| Covalent bonds | 6735 | ||
| Multicenter bonds | 6735 | ||
| Aromaticity | 6735 | ||
| Software | 6736 | ||
| Examples of Applications in Inorganic Chemistry | 6737 | ||
| Multiple Bonds in Inorganic Molecules | 6737 | ||
| Unslipped multiple bonds: Li2B2H4 and OCBBCO | 6737 | ||
| Slipped multiple bonds: Si2H4 and Ga2H22- | 6738 | ||
| Cr-Cr quintuple bonds | 6739 | ||
| The Nature of the XeO Bond | 6739 | ||
| Conclusion | 6740 | ||
| References | 6740 | ||
| Chapter 9.08: Extreme Oxidation States of Transition Metals | 6745 | ||
| Introduction | 6745 | ||
| Choice of Ligands to Stabilize HighOxidation States of Transition Metals | 6746 | ||
| Assignment of Oxidation States | 6747 | ||
| Relativistic Effects and Their Influence on Oxidation States | 6748 | ||
| Quantum-Chemical Description of HighOxidation States | 6751 | ||
| Electron Correlation | 6751 | ||
| Available Methods | 6752 | ||
| Considering Relativistic Effects | 6753 | ||
| Computing Reliable Thermochemistry | 6754 | ||
| Basis sets (DeltaEelec,CBS) | 6754 | ||
| Core-valence correction (DeltaECV) | 6754 | ||
| Relativistic effects (DeltaESR and DeltaESO) | 6754 | ||
| Zero-point energies (DeltaEZPE) | 6754 | ||
| Electron correlation (DeltaECC) | 6755 | ||
| Thermochemistry (SigmaD0) | 6755 | ||
| The electron affinities of the 5d transitionmetal hexafluorides97 | 6755 | ||
| Examples of High and Extreme Oxidation States | 6755 | ||
| A Prominent Example: HgF4 | 6755 | ||
| Does the Oxidation State III of Zinc Exist? | 6756 | ||
| HighValent TransitionMetal Fluorides beyond MF6 | 6757 | ||
| The Case of the Gold Fluorides (and Oxides) | 6758 | ||
| Oxide Compounds of the Group 9 Elements | 6758 | ||
| The IX Oxidation State | 6759 | ||
| Conclusion | 6760 | ||
| Acknowledgments | 6760 | ||
| References | 6760 | ||
| Chapter 9.09: Aromaticity and Antiaromaticity in Inorganic Chemistry | 6763 | ||
| Introduction | 6763 | ||
| What Is Aromaticity and Antiaromaticity? | 6764 | ||
| Aromaticity and Antiaromaticity in Inorganic Main Group Species | 6766 | ||
| Group 1 Elements | 6766 | ||
| sigma-Aromatic Species | 6766 | ||
| sigma-Antiaromatic species | 6767 | ||
| Group 2 Elements | 6767 | ||
| Group 13 Elements | 6768 | ||
| Boron | 6768 | ||
| Doubly-aromatic clusters | 6768 | ||
| Doubly-antiaromatic boron clusters | 6769 | ||
| Boron clusters exhibiting conflicting aromaticity | 6770 | ||
| Aluminum | 6772 | ||
| Gallium | 6774 | ||
| Group 14 Elements | 6775 | ||
| Silicon | 6775 | ||
| Germanium, tin, and lead | 6776 | ||
| Group 15 Elements | 6778 | ||
| Nitrogen | 6778 | ||
| Phosphorus | 6778 | ||
| Arsenic | 6779 | ||
| Antimony | 6780 | ||
| Bismuth | 6780 | ||
| Group 16 Elements | 6781 | ||
| Aromaticity and Antiaromaticity in Transition Metal Species | 6781 | ||
| All-transition Metal Bare Clusters | 6782 | ||
| s-AO-based sigma-aromaticity/antiaromaticity in transition-metal clusters | 6782 | ||
| p-AO-based sigma- and pi-aromaticity/antiaromaticity in transition-metal clusters | 6782 | ||
| d-AO-based sigma-, pi- and delta-aromaticity/antiaromaticity in transition-metal clusters | 6782 | ||
| Aromaticity in Transition-Metal Suboxides | 6784 | ||
| Aromaticity and Antiaromaticity in Transition Metal Carbonyls | 6785 | ||
| Aromaticity in Transition Metal Clusters Embedded in Crystal Lattices and Complex Compounds | 6785 | ||
| Conclusion | 6789 | ||
| Acknowledgments | 6789 | ||
| References | 6789 | ||
| Chapter 9.10: f-Element Complexes | 6795 | ||
| Introduction | 6795 | ||
| Cyclopentadienyl Complexes | 6796 | ||
| Bis(cyclopentadienyl) Complexes | 6796 | ||
| Tris- and Tetrakis(cyclopentadienyl) Complexes | 6799 | ||
| Sandwich Complexes and Derivatives | 6800 | ||
| f-Element COT and Pentalene Complexes | 6800 | ||
| Mixed-Ligand Half-Sandwich Complexes | 6803 | ||
| Chelate Complexes | 6803 | ||
| Azine-Nitrogen Ligands | 6803 | ||
| Bitopic Ligands | 6806 | ||
| More about LnIII-AnIII Differentiation | 6806 | ||
| Metal-Ligand Multiple Bonds | 6812 | ||
| Metal—Nitrogen bonding | 6812 | ||
| Carbene Complexes; Alkylidene (M≡C) and Alkylidyne (M≡C) Bonds | 6812 | ||
| Low-Valent Lanthanide and Actinide Complexes | 6816 | ||
| Inverted-Sandwich Complexes | 6819 | ||
| Metal-Metal Lanthanide and Actinide Bonds | 6820 | ||
| Actinyl Complexes and Derivatives | 6822 | ||
| Physicochemical Properties | 6829 | ||
| Electron Affinity | 6829 | ||
| Magnetic Exchange Coupling | 6829 | ||
| Mixed rare-earth transition-metal complexes | 6829 | ||
| Diuranium complexes | 6831 | ||
| Conclusion | 6832 | ||
| Appendix | 6832 | ||
| List of Used Acronyms | 6832 | ||
| f Atomic Orbitals | 6833 | ||
| Acknowledgments | 6833 | ||
| References | 6833 | ||
| Chapter 9.11: Metal-Metal Bonding | 6839 | ||
| Introduction | 6839 | ||
| The Quadruple Bond: Electronic Structure of [Re2Cl8]2- | 6840 | ||
| The Quintuple Bond: ArCr≡CrAr | 6842 | ||
| Transition-Metal Diatomics | 6845 | ||
| Metal-Metal Bonding in the Face-Shared Bioctahedral M2X9 Family | 6846 | ||
| Metal-Metal Bonding in Extended Metal Atom Chains (EMACs) | 6848 | ||
| Metal-Metal Bonding in Low-Valent Carbonyls | 6850 | ||
| Metal-Metal Bonds between f-Block Elements | 6852 | ||
| Metal-Metal Bonding in Main-Group Elements | 6854 | ||
| Conclusion | 6856 | ||
| References | 6856 | ||
| Chapter 9.12: Weak Hydrogen Bonding | 6859 | ||
| Introduction | 6859 | ||
| Computational Methods | 6860 | ||
| Different Kinds of Weak Hydrogen Bonds in Organic and Inorganic Systems | 6861 | ||
| Y-H⋯A. A and Y are Not Simultaneously Very Electronegative Elements | 6861 | ||
| Y-H⋯π . They Involve One Y-H Bond and the Electrons of Rings or Multiple Bonds | 6863 | ||
| Y-H⋯M Interactions and How They Dffer from Agostic Interactions | 6868 | ||
| X-H⋯H-M and X-H⋯H-B: The Dihydrogen Bond | 6869 | ||
| Hydrogen Bonds or Not? The `Homonuclear Hydrogen Bond´ C—H...H-C or M—H..H-m | 6871 | ||
| Conclusion | 6872 | ||
| Acknowledgment | 6872 | ||
| References | 6872 | ||
| Spectroscopy | 6877 | ||
| Chapter 9.13: Electron Paramagnetic Resonance | 6877 | ||
| EPR Parameters from Experiments | 6878 | ||
| Spins and Magnetic Moments | 6878 | ||
| Interaction of Spins with Magnetic Fields: The g-Tensor | 6878 | ||
| The Effect of Magnetic Nuclei: Hyperfine Coupling | 6879 | ||
| Systems with More Than One Unpaired Electron: The Zero-Field Splitting | 6880 | ||
| Hyperfine Coupling from Quantum Chemistry: Nonrelativistic Approach | 6880 | ||
| g-Tensors from Quantum Chemistry | 6884 | ||
| Hyperfine Coupling from Quantum Chemistry: Relativistic Contributions | 6887 | ||
| ZFS from Quantum Chemistry | 6888 | ||
| DFT Calculations of the Hyperfine Coupling Tensors | 6888 | ||
| Ab initio Post-Hartree-Fock Calculations of HFCCs | 6892 | ||
| DFT Calculations of g-Tensors | 6893 | ||
| Ab initio Post-Hartree-Fock Calculations of g-tensors | 6894 | ||
| DFT Calculations of ZFS | 6894 | ||
| Ab initio Calculations of ZFS | 6895 | ||
| Conclusion | 6896 | ||
| Acknowledgments | 6897 | ||
| References | 6897 | ||
| Chapter 9.14: NMR Spectroscopy in Inorganic Chemistry | 6899 | ||
| Generalities on Nuclear Magnetic Resonance Spectroscopy | 6899 | ||
| Introduction to Magnetic Resonance | 6899 | ||
| Nuclear Magnetic Resonance Spectroscopy | 6900 | ||
| Introduction to the NMR Parameter Calculations | 6904 | ||
| Quantum Mechanical Calculation of NMR Parameters | 6906 | ||
| Variational Perturbation Theory | 6906 | ||
| Application to Hartree-Fock and Kohn-Sham Theories | 6907 | ||
| Induced Current Density and Periodic Conditions | 6909 | ||
| Gauge-Origin Problem | 6910 | ||
| DFT Calculation of NMR Shieldings | 6911 | ||
| Basis Set Completeness | 6911 | ||
| Electron Correlation | 6911 | ||
| Density Functional Theory | 6912 | ||
| Relativistic Effects | 6914 | ||
| Illustrative Example in Solid-State NMR | 6915 | ||
| Experimental Conditions and Simulation | 6917 | ||
| Some Considerations on the Theoretical Accuracy | 6920 | ||
| Conclusion | 6921 | ||
| Acknowledgment | 6922 | ||
| References | 6922 | ||
| Chapter 9.15: Calculating Electronic Optical Activity of Coordination Compounds | 6925 | ||
| Introduction | 6925 | ||
| Electronic Optical Activity: CD and ORD | 6926 | ||
| OR Parameter and Rotatory Strength | 6926 | ||
| Line Shapes, ORD, Kramers-Kronig Transforms | 6927 | ||
| Approximate Wavefunction Theories and TDDFT | 6928 | ||
| Representative Examples: Lambda-[Co(en)3]3+, Lambda-[Co(Acac)3], and Lambda-[Os(Phen)3]2 | 6929 | ||
| The Origin of CD in LF and LMCT Transitions | 6931 | ||
| Geometrical Considerations, Metal Symmetry Orbitals, TDDFT Analysis | 6931 | ||
| LF Transitions | 6933 | ||
| LMCT Transitions | 6934 | ||
| Effects due to Changes in the Chelate Ring Conformation | 6934 | ||
| Ligands with pi Orbitals | 6934 | ||
| Exciton Coupling CD in Metal Complexes | 6935 | ||
| Survey of TDDFT Computations of Electronic Optical Activity | 6938 | ||
| Conclusion | 6943 | ||
| Acknowledgments | 6943 | ||
| References | 6943 | ||
| Chapter 9.16: X-Ray Spectroscopy | 6945 | ||
| Introduction | 6945 | ||
| X-Ray Spectra and Data Interpretation | 6946 | ||
| Ligand K-Edge Spectra | 6946 | ||
| Metal K-Edge Spectra | 6946 | ||
| Metal L-Edge Spectra | 6947 | ||
| X-Ray Emission | 6947 | ||
| EXAFS | 6948 | ||
| Experimental Methods | 6949 | ||
| Theoretical Calculation of X-Ray Spectra | 6950 | ||
| General Considerations | 6950 | ||
| Transition energies | 6951 | ||
| Transition intensities | 6951 | ||
| Spin-orbit coupling | 6951 | ||
| Continuum states | 6951 | ||
| The rising edge | 6951 | ||
| Time-Dependent DFT | 6952 | ||
| Ligand K-Edge Spectra | 6952 | ||
| Metal K-Edge Spectra | 6953 | ||
| Metal L-Edge Spectra | 6953 | ||
| X-Ray Emission | 6955 | ||
| Conclusion | 6957 | ||
| References | 6957 | ||
| Relevant Website | 6957 | ||
| Spins and Magnetism | 6959 | ||
| Chapter 9.17: Spin State and Stereochemistry | 6959 | ||
| Introduction | 6959 | ||
| Bonding in Coordination Compounds | 6960 | ||
| MO Theory | 6960 | ||
| Factors Affecting the Splitting of the d-Orbitals | 6963 | ||
| Spin State | 6964 | ||
| Stereochemistry and Spin State | 6966 | ||
| Stereospin Isomerism | 6966 | ||
| Continuous Shape Measures | 6966 | ||
| Coordination Number Two | 6968 | ||
| Coordination Number Three28 | 6968 | ||
| Coordination Number Four | 6969 | ||
| Coordination Number Five | 6974 | ||
| Coordination Number Six | 6976 | ||
| Enforcing Unusual Spin States | 6979 | ||
| Spin Pairing in the Nonbonding d-Orbitals | 6979 | ||
| Low-Spin Tricoordination | 6979 | ||
| Low-Spin Tetracoordination | 6980 | ||
| Selecting the Spin State in Tetracoordination | 6982 | ||
| Conclusion | 6983 | ||
| References | 6984 | ||
| Chapter 9.18: Theoretical Approaches for Spin-Crossover Phenomenon in Transition-Metal Complexes | 6987 | ||
| Introduction: General Notions About the Spin Crossover | 6987 | ||
| Quantum-Chemical Studies of SCO Systems | 6989 | ||
| Ab Initio Calculations of SCO Systems | 6989 | ||
| DFT Calculations of SCO Complexes | 6990 | ||
| Quantum Chemistry of SCO Systems in Solid State | 6993 | ||
| Physical Models of the SCO Phenomenon | 6995 | ||
| Structure-Property Relationship in SCO Compounds | 6996 | ||
| Conclusion | 6997 | ||
| References | 6997 | ||
| Chapter 9.19: Spin Crossover Reactivity | 6999 | ||
| Introduction | 6999 | ||
| Early Work | 7000 | ||
| Development of Rational Schemes | 7001 | ||
| Crossover or Not: Relevance of Ligand Field and Pairing Energy | 7003 | ||
| Minimum Energy Crossing Point | 7005 | ||
| The Forbiddenness Factor | 7006 | ||
| The Spin-Acceleration Concept | 7007 | ||
| Spin-Block or No Spin-Block? The Spin Crossover Junction | 7009 | ||
| Effect of the Chemical Environment on the Reaction Rates | 7013 | ||
| Effect of Spin Crossover on Selectivities | 7015 | ||
| Role of Spin Crossover in More Complex Mechanisms | 7015 | ||
| Conclusion | 7017 | ||
| References | 7017 | ||
| Chapter 9.20: Exchange Coupling in Di- and Polynuclear Complexes | 7019 | ||
| Introduction | 7020 | ||
| Spin Hamiltonians and Experimental Determination of the Exchange Coupling Constants | 7021 | ||
| Qualitative Models for the Exchange Interactions | 7023 | ||
| DFT Methods to Evaluate Exchange Coupling Constants | 7027 | ||
| Post-HF Methods to Calculate Exchange Coupling Constants | 7032 | ||
| First-Row Transition-Metal Complexes | 7034 | ||
| Early First-Row Elements | 7034 | ||
| Middle First-Row Elements | 7037 | ||
| Dinuclear complexes | 7037 | ||
| Polynuclear complexes | 7040 | ||
| Late First-Row Elements | 7044 | ||
| Dinuclear complexes | 7044 | ||
| Polynuclear complexes | 7049 | ||
| Second- and Third-Row Transition-Metal Complexes | 7053 | ||
| Lanthanoids and Actinoids | 7056 | ||
| Conclusion | 7058 | ||
| References | 7059 | ||
| Relevant Websites | 7067 | ||
| Bioinorganic Systems | 7069 | ||
| Chapter 9.21: [Fe]-, [Ni-Fe]-, and [Fe-Fe]-Hydrogenases | 7069 | ||
| Introduction | 7069 | ||
| Classes of Hydrogenases | 7070 | ||
| An Overview of Quantum Mechanical Methods | 7070 | ||
| Hybrid QM/MM Methods | 7072 | ||
| The Potential Energy Surface | 7072 | ||
| Catalytic Mechanisms of Hydrogenases | 7073 | ||
| Nickel-Iron Hydrogenases | 7073 | ||
| Ni-A and Ni-B states | 7073 | ||
| Activation of the Ni-B (ready) and Ni-A (unready) states | 7074 | ||
| Structure of the intermediates in the catalytic cycle | 7074 | ||
| Spin state of Ni-SI and binding of H2 | 7075 | ||
| The catalytic mechanism | 7075 | ||
| An autocatalytic mechanism for Ni-Fe | 7076 | ||
| Nickel-iron-selenium hydrogenases | 7076 | ||
| Iron Hydrogenase | 7076 | ||
| Structure | 7076 | ||
| Synthetic models | 7077 | ||
| Mechanism | 7077 | ||
| Computational studies | 7078 | ||
| Iron-Iron [Fe-Fe]-Hydrogenases | 7079 | ||
| Oxidation states present in Fe-Fe hydrogenases | 7079 | ||
| Theoretical simulations | 7080 | ||
| QM/MM studies | 7082 | ||
| Conclusion | 7084 | ||
| References | 7084 | ||
| Chapter 9.22: Molybdenum- and Tungsten-Mediated Oxidations | 7087 | ||
| Introduction | 7087 | ||
| Trigonal Prismatic Versus Orthorhombic Geometry of Molybdenum in the DMSOR Family | 7089 | ||
| The Role of the MPT Ligand | 7091 | ||
| Understanding and Assigning Spectroscopic Data | 7094 | ||
| Photoelectron Spectroscopy and Insights into the Dithiolene-Sulfur-Metal Bond | 7094 | ||
| Magnetic Circular Dichroism, Electron Paramagnetic Resonance Spectroscopy, and XAS on the Sulfur K Edge and the DMSO Red ... | 7096 | ||
| EPR Plus Electron Absorption Spectroscopy and Carbon-Hydrogen Bond Activation by XO | 7098 | ||
| X-Ray Absorption and EPR Spectroscopy and a Clinical Mutant of SO | 7100 | ||
| Elucidating Reaction Mechanisms | 7101 | ||
| DMSOR Family Reactions | 7101 | ||
| SO Family Reactions | 7103 | ||
| XO Family Reactions | 7103 | ||
| Tungsten Enzyme's Reactions | 7104 | ||
| Exotic Enzymes and Reactions | 7105 | ||
| Conclusion | 7107 | ||
| References | 7107 | ||
| Chapter 9.23: Nitrogenase and Nitrogen Activation | 7111 | ||
| Introduction | 7111 | ||
| Scope and Organization of This Chapter | 7111 | ||
| Structure and Function of Nitrogenase | 7112 | ||
| Fe-Protein Cycle | 7112 | ||
| Metal Clusters within the MoFe-Protein | 7113 | ||
| Thorneley-Lowe Cycle | 7113 | ||
| Site-Directed Mutagenesis Experiments | 7113 | ||
| Trapping and Characterization of Intermediates of N2 Reduction by Electron Paramagnetic Resonance Spectroscopy | 7114 | ||
| DFT Treatments of N2 Reduction in Model Systems | 7114 | ||
| General Considerations | 7114 | ||
| Schrock Cycle | 7115 | ||
| Chatt Cycle | 7118 | ||
| Reduction and Protonation of N2 at Cubane Clusters | 7119 | ||
| Reduction and Protonation of N2 at Iron Complexes | 7120 | ||
| DFT Calculations on the FeMoco and Its Reactivity with N2 | 7121 | ||
| Theoretical Treatments before Discovery of X | 7121 | ||
| Noodleman et al. | 7121 | ||
| Nrskov et al. | 7124 | ||
| Theoretical Treatments after Discovery of X | 7125 | ||
| Noodleman et al. | 7125 | ||
| Nrskov et al. | 7125 | ||
| Blöchl et al. | 7128 | ||
| Dance | 7131 | ||
| Further theoretical studies | 7132 | ||
| Conclusion | 7133 | ||
| Acknowledgments | 7134 | ||
| Note added in proof | 7134 | ||
| References | 7134 | ||
| Chapter 9.24: Oxygen Atom Transfer | 7137 | ||
| Introduction | 7137 | ||
| Enzymatic Oxygen Atom Transfer | 7137 | ||
| Heme Enzymes | 7138 | ||
| Nonheme Enzymes | 7141 | ||
| Computational Studies on Oxygen Atom Transfer | 7141 | ||
| Compound I | 7143 | ||
| Two-State Reactivity | 7144 | ||
| Aliphatic hydroxylation | 7145 | ||
| Epoxidation | 7148 | ||
| Sulfoxidation | 7148 | ||
| Aromatic hydroxylation | 7149 | ||
| Conclusion | 7150 | ||
| References | 7150 | ||
| Organometallic Chemistry and Catalysis | 7153 | ||
| Chapter 9.25: Mechanistic Studies of CX Bond Activation at Transition-Metal Centers | 7153 | ||
| Glossary | 7154 | ||
| Introduction | 7154 | ||
| C—C Bond Activation | 7155 | ||
| At Neutral Atoms | 7155 | ||
| C—C Bond Activation at Transition-Metal Cations | 7158 | ||
| C—C Bond Activation at Molecular Complexes | 7160 | ||
| Model systems: early studies | 7160 | ||
| At d10 [MLn] transition-metal complexes | 7161 | ||
| Model studies at d8 [MLn] transition-metal complexes | 7162 | ||
| Modeling experimentally observed C—C bond activation | 7164 | ||
| Intramolecular C—C bond activation | 7164 | ||
| Stable C—C sigma-complexes as precursors to C—C activation | 7167 | ||
| C—C bond activation of strained cycloalkanes | 7168 | ||
| CCN bond activation | 7168 | ||
| C—X Bond Activation (X=Group 13) | 7171 | ||
| Oxidative Addition | 7171 | ||
| Transmetallation | 7172 | ||
| C—X Bond Activation (X=Group 14 Other than C) | 7173 | ||
| Oxidative Addition | 7173 | ||
| Transmetallation | 7175 | ||
| C—X Bond Activation (X=Group 15) | 7176 | ||
| C(sp3)—X Activation | 7176 | ||
| C(sp2)—X Activation | 7177 | ||
| With Cationic Substrates | 7177 | ||
| C—X Bond Activation (X=Group 16) | 7178 | ||
| At Transition-Metal Cations | 7178 | ||
| At Molecular Complexes | 7178 | ||
| C(sp3)—O/S bond activation | 7178 | ||
| C(sp2)—O/S bond activation | 7179 | ||
| S—CN bond activation | 7183 | ||
| C—F Bond Activation | 7184 | ||
| At Transition-Metal Atoms | 7184 | ||
| At Metal Cations | 7184 | ||
| At lanthanide cations | 7185 | ||
| At late transition-metal cations | 7186 | ||
| At Molecular Complexes | 7186 | ||
| C(sp3)—F bond activation | 7186 | ||
| Aromatic C(sp2)—F bond activation | 7188 | ||
| Oxidative addition | 7188 | ||
| Ligand-assisted C—F activation | 7190 | ||
| Other mechanisms | 7193 | ||
| Alkenyl and alkynyl C—F bond activation | 7195 | ||
| C—X Bond Activation (X=Group 17 Other Than F) | 7195 | ||
| At Transition-Metal Atoms | 7195 | ||
| At Transition-Metal Cations | 7195 | ||
| C(sp3)—X Bond Activation at Molecular Complexes | 7196 | ||
| At group 9 metal centers | 7196 | ||
| At group 10 metal centers | 7197 | ||
| At group 11 metal centers | 7198 | ||
| C(sp2)—X Bond Activation at Molecular Complexes | 7198 | ||
| At group 9 metal centers | 7199 | ||
| At group 10 metal centers | 7200 | ||
| At neutral [PdL2] species (L=monodentate ligands) | 7200 | ||
| At bidentate [Pd(L—L)] systems | 7200 | ||
| At mono-ligated [Pd(L)] | 7201 | ||
| At anionic [Pd(0)YLn]- | 7204 | ||
| At `ligand-free´ Pd(0) | 7205 | ||
| Heterocyclic C—X bond activation at Pd(0) | 7206 | ||
| Alkenyl C(sp2)—X activation at Pd | 7207 | ||
| At Pd(II) metal centers | 7207 | ||
| At other group 10 metal centers | 7207 | ||
| At group 11 metal centers | 7208 | ||
| Conclusion | 7210 | ||
| References | 7210 | ||
| Chapter 9.26: Theoretical Studies on the Reaction Mechanism of Metal-Assisted CH Activation | 7213 | ||
| Introduction | 7213 | ||
| σ-Bond Metathesis by Early Transition Metals | 7214 | ||
| The 1,2-Addition Mechanism | 7216 | ||
| Oxidative Addition by d4-d10 Species | 7219 | ||
| Nonclassical Mechanisms | 7223 | ||
| The Thermochemistry of C—H Activation | 7225 | ||
| Chelate-Assisted C—H Activation | 7226 | ||
| Base- and Ligand-Assisted C—H Activation | 7226 | ||
| The Rebound Mechanism | 7229 | ||
| Bare Metal-Oxygen Systems | 7230 | ||
| C—H Oxidation by Inorganic Reagents | 7231 | ||
| The Shilov Reaction | 7233 | ||
| C—H Oxidation by Fe, Mn, and Cu Biomimetics | 7236 | ||
| Conclusion | 7241 | ||
| References | 7242 | ||
| Chapter 9.27: H-H Bond Activation | 7245 | ||
| Introduction and Scope | 7246 | ||
| Dihydrogen Complexes | 7247 | ||
| General Concepts of Dihydrogen Complexes | 7247 | ||
| What Is New in Dihydrogen Complexes (2001-11)? | 7249 | ||
| First-row dihydrogen complexes | 7250 | ||
| New ligands | 7250 | ||
| Bis(dihydrogen) complexes | 7251 | ||
| Paramagnetic dihydrogen complexes | 7251 | ||
| The Problem of Determining the H-H Distance | 7252 | ||
| Diffraction studies | 7252 | ||
| DFT calculations | 7252 | ||
| NMR studies | 7253 | ||
| Reactivity of Dihydrogen Complexes | 7254 | ||
| From Dihydrogen to Dihydride: Homolytic Splitting of H2 | 7254 | ||
| The OA Pathway | 7254 | ||
| Dihydrogen or Dihydride? | 7254 | ||
| Looking at the H-H Rupture | 7258 | ||
| H2 Activation by Nonmetal Centers | 7258 | ||
| Neither Dihydrogen Nor Dihydride | 7259 | ||
| Elongated Dihydrogen and Compressed Dihydride Complexes | 7260 | ||
| Hydrogen Delocalization in Polyhydrides: Where Are the Hydrogens? | 7262 | ||
| From Dihydrogen to a Hydride and a Proton: Heterolytic Splitting of H2 | 7263 | ||
| Metal-Mediated Heterolytic H2 Cleavage: Reactivity of Coordinated Dihydrogen | 7264 | ||
| Deprotonation by an external neutral base or an anion | 7264 | ||
| Intramolecular heterolytic cleavage of H2 | 7265 | ||
| H2 activation in water | 7267 | ||
| H2 heterolytic splitting in catalytic hydrogenations | 7268 | ||
| H2 Heterolytic Cleavage in Metal-Free Systems: Reactivity of Frustrated Lewis Pairs (FLPs) | 7272 | ||
| Experimental playground of frustrated Lewis pairs | 7272 | ||
| How does it really work? Theoretical insights into the mechanisms of H2 activation mediated by FLP | 7274 | ||
| Re-Forming the H-H Bond: Hydride Protonation | 7276 | ||
| General Overview of the Mechanism | 7276 | ||
| Dihydrogen Bonding | 7276 | ||
| The Donor and Acceptor Influences | 7277 | ||
| External Effects on the Protonation Process | 7280 | ||
| Conclusion | 7281 | ||
| References | 7282 | ||
| Chapter 9.28: C—C Bond Formation | 7285 | ||
| Introduction and Scope | 7285 | ||
| The Nature of C—C Bonds | 7286 | ||
| C—C Bond Types | 7286 | ||
| Transition Metal Complexes as Catalysts in C—C Bond Formation | 7287 | ||
| Generating C-C Single Bonds: Cross-Coupling Reactions | 7288 | ||
| Catalytic Cycle for C—C Cross-Coupling Reactions | 7288 | ||
| Common Reaction Steps: Oxidative Addition and Reductive Elimination | 7289 | ||
| The oxidative addition step | 7289 | ||
| The reductive elimination step | 7291 | ||
| The Transmetalation Step | 7293 | ||
| Suzuki-Miyaura reaction | 7294 | ||
| Stille reaction | 7298 | ||
| Negishi reaction | 7301 | ||
| Sonogashira reaction | 7303 | ||
| Generating C═C Double Bonds: The Olefin Metathesis Reaction | 7306 | ||
| Heterogeneous Alkene Metathesis Catalysts | 7309 | ||
| Classical heterogeneous catalysts | 7309 | ||
| Heterogenized molecular catalysts | 7310 | ||
| Homogeneous Mo and W-Based Schrock-Type Alkylidenes | 7311 | ||
| The early works on ill-defined and symmetric molybdenum imido bisalkoxy alkylidene complexes | 7311 | ||
| Catalytic activity of the dissymmetric d0 alkylidene complexes | 7311 | ||
| Catalyst deactivation and byproduct formation | 7312 | ||
| Homogeneous Ru-Based Grubbs-Type Carbenes | 7313 | ||
| Catalytic activity in olefin metathesis | 7313 | ||
| Catalyst deactivation mechanisms | 7315 | ||
| Understanding Ru-based catalyst selectivity | 7316 | ||
| Conclusion | 7317 | ||
| References | 7319 | ||
| Chapter 9.29: Enantioselective Synthesis | 7325 | ||
| Introduction | 7325 | ||
| A Theory for Enantioselective Catalysis | 7326 | ||
| Computational Methods for Enantioselective Catalysis | 7328 | ||
| Quantum Mechanics, Molecular Mechanics, QM/MM | 7328 | ||
| Quantum to Molecular Mechanics | 7329 | ||
| Conformational Search | 7330 | ||
| Molecular Descriptors | 7330 | ||
| Applications | 7332 | ||
| Rhodium-Catalyzed Hydrogenation of Enamides | 7332 | ||
| Osmium-Catalyzed Dihydroxylation of Olefins | 7334 | ||
| Zinc-Catalyzed Alkylation of Aldehydes | 7338 | ||
| Copper-Catalyzed Cyclopropanation | 7341 | ||
| Metal-Catalyzed Sulfoxidation | 7344 | ||
| Conclusion | 7347 | ||
| References | 7347 | ||
| Clusters and Large Molecules | 7351 | ||
| Chapter 9.30: Main Group Metal Clusters | 7351 | ||
| Introduction | 7351 | ||
| Group 13 Clusters | 7352 | ||
| Small Boron Clusters (Bn, n=2-14): Aufbau Principle | 7352 | ||
| Elemental clusters | 7352 | ||
| Convex and quasiplanar clusters | 7353 | ||
| Three-dimensional clusters | 7354 | ||
| Medium-Sized Boron Clusters (Bn, n=15-20): A 2D-3D Structural Transition | 7355 | ||
| Structures of Allotropes of Boron: Electron-Counting Rule | 7358 | ||
| Wade's rule | 7359 | ||
| mno Rule | 7359 | ||
| α-Rhombohedral boron | 7360 | ||
| beta-Rhombohedral boron | 7361 | ||
| Boron Fullerenes | 7365 | ||
| Stuffed fullerene-like boron clusters | 7366 | ||
| Aluminum Clusters | 7371 | ||
| Stability of the clusters | 7373 | ||
| Electronic structure | 7375 | ||
| Superatom Clusters | 7376 | ||
| Aluminum clusters as superatoms mimicking inert gas atoms | 7376 | ||
| Aluminum clusters as superatoms mimicking alkaline metal atoms | 7378 | ||
| Gallium Clusters | 7380 | ||
| Gan clusters (n=2-8) | 7380 | ||
| Gan clusters (n=9-25) | 7382 | ||
| Conclusion | 7383 | ||
| References | 7384 | ||
| Chapter 9.31: Theoretical Treatment of Ligated Clusters Containing Transition Metals | 7387 | ||
| Introduction | 7387 | ||
| Qualitative Theoretical Approach | 7388 | ||
| Electron-Counting Rules | 7388 | ||
| The closed-shell principle | 7388 | ||
| The effective atomic number rule and its limitation in cluster chemistry | 7388 | ||
| Electron counting in inorganic cluster chemistry | 7389 | ||
| Selected Examples of Stable Inorganic Clusters Containing Transition Metals Which Satisfy Electron-Counting Rules | 7390 | ||
| Exploring the Limits of Electron-Counting Rules | 7394 | ||
| Where are the limits? | 7394 | ||
| Clusters diverging from spherical shape | 7394 | ||
| Clusters with open-shell configurations | 7397 | ||
| Quantitative Theoretical Approach | 7398 | ||
| Quantum Computational Tools | 7398 | ||
| Large Ligated Metal Clusters Versus Nanoparticles | 7398 | ||
| The Role of the Surrounding Ligands in Ligated Metal Clusters | 7399 | ||
| Conclusion | 7400 | ||
| References | 7401 | ||
| Chapter 9.32: Structure and Reactivity of Polyoxometalates | 7405 | ||
| Introduction | 7405 | ||
| Classification of POMs | 7406 | ||
| The Keggin Anion | 7407 | ||
| Electronic Structure of Mixed Anions | 7407 | ||
| POMs as Multidentate Ligands | 7408 | ||
| α-Keggin and W-D Anions Containing TM Ions | 7409 | ||
| Imido, Nitrido, and Organic Derivatives | 7410 | ||
| Basicity of Superficial Oxygen Atoms | 7412 | ||
| Acid Catalysis | 7413 | ||
| Catalytic Oxidations: Alkene Epoxidation and Oxygen Transfer Reactions | 7414 | ||
| H2O2-Based Alkene Epoxidation by Early-TM-Based POMs | 7415 | ||
| Monoxygenations by Late-TM-Substituted POMs | 7417 | ||
| Water Splitting | 7418 | ||
| Conclusion | 7422 | ||
| Acknowledgments | 7422 | ||
| References | 7422 | ||
| Chapter 9.33: Endohedral Fullerenes | 7425 | ||
| Introduction | 7425 | ||
| Isomers, Steric Energy, and the Isolated Pentagon Rule | 7427 | ||
| Small Endohedral Fullerenes (M@C2n; 2n=28, 32, 36, and 44) | 7427 | ||
| Encapsulation of Atoms and Small Molecules in C60 | 7429 | ||
| Icosahedral C80: A Hosting Cage for Clusters with 6e-Transfer | 7430 | ||
| EMFs Based on the C82 Cage: M2C2@C82, Sc2X@C82 (X=O and S) | 7433 | ||
| Larger Cages: The Role of Cluster Size | 7434 | ||
| Middle- and Large-Sized Monometallic and Dimetallic Endohedral Fullerenes | 7435 | ||
| Violations of the IPR Rule for Fullerenes Larger Than C60 | 7437 | ||
| Reactivity of Endohedral Fullerenes | 7437 | ||
| Conclusion | 7440 | ||
| Acknowledgments | 7440 | ||
| References | 7440 | ||
| Chapter 9.34: Nanotubes and Peapods | 7443 | ||
| Introduction | 7443 | ||
| Inorganic NTs | 7445 | ||
| Classification and Structural Models | 7445 | ||
| NTs Based on BN and Its Analogs | 7446 | ||
| Boron-Based NTs | 7449 | ||
| NTs Based on Silicon and Germanium | 7449 | ||
| NTs Based on Group 15 Elements | 7449 | ||
| NTs Based on Metal Chalcogenides | 7450 | ||
| NTs Based on Oxides | 7450 | ||
| Functionalization of NTs | 7451 | ||
| Exohedral versus Endohedral Functionalization | 7451 | ||
| Filling Chemistry | 7453 | ||
| C60 Peapods | 7453 | ||
| Higher Fullerenes and Other Molecules | 7455 | ||
| Peapods Based on Inorganic NTs | 7455 | ||
| Conclusion | 7456 | ||
| References | 7456 | ||
| Solid State Compounds | 7459 | ||
| Chapter 9.35: Structure Prediction in Solid-State Chemistry as an Approach to Rational Synthesis Planning | 7459 | ||
| Introduction | 7460 | ||
| The Energy Landscape Concept: Configuration Space, Barriers, Lifetimes, and Local Ergodicity | 7461 | ||
| Computational Tools for the Exploration of Chemical Energy Landscapes: Search Strategies and Cost Functions | 7462 | ||
| General Aspects of Search Strategies | 7462 | ||
| Algorithms for Global Landscape Explorations | 7464 | ||
| Identification of local minima | 7464 | ||
| Simulated annealing | 7464 | ||
| Taboo searches and lid-based optimizations | 7465 | ||
| Genetic and evolutionary optimization | 7465 | ||
| Deterministic and multiple-quench optimizations | 7466 | ||
| Identification of locally ergodic regions at elevated temperatures | 7466 | ||
| Analysis of the barrier structure: Saddle points, transition paths, and probability flow | 7466 | ||
| Approximate Description of the Energy Landscape and Cost Functions | 7467 | ||
| Ab initio energy landscapes | 7467 | ||
| Empirical potential landscapes | 7468 | ||
| Cost function landscapes | 7468 | ||
| Structure Analysis Tools: SymmetrieFiNDer, RaumGruppenSucher, and CoMPare Zelle | 7469 | ||
| Moving to Thermodynamic Space: DOSs, Free Enthalpy, and Phase Diagrams from First Principles | 7469 | ||
| Measurement of Local and Global DOSs | 7469 | ||
| Computation of Free Enthalpy | 7470 | ||
| Phase Diagrams from First Principles Incorporating Metastable Phases | 7470 | ||
| Examples | 7471 | ||
| Illustrative Methodological Examples | 7471 | ||
| Modular approach: Study of the alkali halides | 7471 | ||
| Tree graph landscape representation: The landscapes of MgF2 and CaF2 | 7472 | ||
| Free energy tree graph representation: The landscape of SrO | 7472 | ||
| Multinary phase diagrams: The quasi-ternary semiconductor (Al,In,Ga)–Sb and similar systems | 7472 | ||
| Structure prediction in multinary systems: Study of the alkali metal orthocarbonates M4(CO4), with M=Li, Na, K, R | 7473 | ||
| Structure Prediction and Structure Determination Using Global Landscape Exploration: Overview and Presentation of S | 7474 | ||
| Elemental modifications | 7474 | ||
| Ionic compounds | 7474 | ||
| Intermetallic solids | 7475 | ||
| Covalent solids | 7476 | ||
| Compounds exhibiting two or more types of bonding | 7476 | ||
| Molecular crystals | 7477 | ||
| General aspects | 7477 | ||
| Examples | 7477 | ||
| Zeolites | 7478 | ||
| Selected examples of structure determination | 7479 | ||
| Feasibility and Experimental Verification | 7479 | ||
| Prediction and Synthesis of Sodium Nitride Na3N | 7480 | ||
| Prediction and Synthesis of Metastable Lithium Halides LiX (X=I, Br, Cl) | 7480 | ||
| Prediction and Validation of High-Pressure Alkali Metal Sulfides | 7481 | ||
| Outlook | 7481 | ||
| Future Developments of Exploration Algorithms | 7481 | ||
| Rational Development of Synthesis Routes | 7482 | ||
| Acknowledgments | 7483 | ||
| References | 7483 | ||
| Chapter 9.36: Structure and Vibrational Spectra | 7489 | ||
| Introduction | 7489 | ||
| Equilibrium Structure | 7490 | ||
| Vibrational Properties: Computational Aspects | 7491 | ||
| Lattice Dynamics | 7491 | ||
| Born Charges | 7492 | ||
| IR Intensity and Dielectric Tensors | 7492 | ||
| Nonanalytical Contribution and LO Modes | 7492 | ||
| Anharmonicity | 7492 | ||
| Reflectance Spectrum | 7493 | ||
| Simulation of Vibrational Properties | 7493 | ||
| Computational Parameters | 7494 | ||
| Choice of the Hamiltonian | 7494 | ||
| Effect of the Basis Set | 7495 | ||
| IR Spectrum and TO-LO Splitting | 7497 | ||
| Reflectance Spectrum | 7499 | ||
| Raman Spectrum | 7500 | ||
| Tools for the Interpretation of Spectra and Mode Analysis | 7501 | ||
| Conclusion | 7504 | ||
| References | 7504 | ||
| Relevant Websites | 7505 | ||
| Chapter 9.37: Adsorption in Metal-Organic Frameworks | 7507 | ||
| Introduction | 7507 | ||
| Modeling Adsorbents | 7508 | ||
| Framework Composition | 7508 | ||
| Framework Size | 7509 | ||
| Framework Flexibility | 7510 | ||
| Extraframework Ions | 7511 | ||
| Surface Areas and Pore Volumes | 7511 | ||
| Modeling Adsorbates | 7513 | ||
| Most Common Models for Nonpolar Molecules in MOFs | 7514 | ||
| Most Common Models for Polar Molecules | 7514 | ||
| Modeling Adsorbent-Adsorbate Interactions | 7515 | ||
| van der Waals and Coulombic Interactions | 7515 | ||
| QM Calculations | 7515 | ||
| Classic Methods to Compute Adsorption in MOFs | 7516 | ||
| Henry Coefficients | 7517 | ||
| Energies and Entropies of Adsorption | 7517 | ||
| Adsorption Isotherms of Single Components | 7518 | ||
| Comparison of computed isotherms with experiment | 7519 | ||
| Adsorption Isotherms of Mixtures | 7519 | ||
| The ideal adsorbed solution theory | 7520 | ||
| Effective MC scheme for multicomponent gas adsorption | 7521 | ||
| Conclusion | 7521 | ||
| Acknowledgments | 7522 | ||
| References | 7522 | ||
| Chapter 9.38: Electronic Conductivity of Solids | 7525 | ||
| Introduction | 7525 | ||
| Electronic Conduction | 7526 | ||
| The Free-Electron Model for Metals | 7526 | ||
| One-dimensional case | 7526 | ||
| Effect of an electric field | 7526 | ||
| Generalization to 3D systems | 7527 | ||
| Band Theory of Solids | 7528 | ||
| Actual crystal structure and gap opening | 7528 | ||
| Fermi surface and dimensionality | 7530 | ||
| Which Factors Influence Conductivity? | 7531 | ||
| Real Solids: The Links between Structural, Chemical, and Conductivity Properties | 7533 | ||
| Activated versus Nonactivated Conductivity | 7533 | ||
| Anisotropy: Structural versus Electronic | 7541 | ||
| Metal-to-Insulator Transitions | 7546 | ||
| Fermi Surface Instabilities | 7546 | ||
| Electronic Localization | 7548 | ||
| Conclusion | 7550 | ||
| References | 7551 | ||
| Relevant Websites | 7552 | ||
| Index | 7553 |