- 巻冊次
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2 ISBN 9783527308118
内容説明
Written specifically for scientists seeking an insight into this field outside of their own specific area of focus, this series offers a truly comprehensive overview of every area in inorganic chemistry.
In this second volume, the editors have assembled an international team of experts who provide an unparalleled look at their latest research results in:
reaction mechanisms
aluminum(I) chemistry
solid state chemistry
transition metals
structural chemistry
and many related topics.
For everyone wanting to stay abreast of developments in this increasingly specialized field.
目次
- Preface xiii
List of Contributors xv
1 On the Track of Reaction Mechanisms: Characterization and Reactivity of Metal Atom Dimers 1
Hans-Joerg Himmel
1.1 Introduction 1
1.2 Principle and Realization of the Matrix-Isolation Experiment 2
1.3 Characterization of Metal Atom Dimers 3
1.4 Reactivity of Metal Atom Dimers and Comparison with the Reactivity of Single Metal Atoms 7
1.4.1 The Reaction Between Ga2 and H2 7
1.4.2 The Reaction Between Ti2 and N2 10
1.5 Concluding Remarks 12
References 12
2 Noble Gas Hydride Compounds 15
Mika Pettersson, Leonid Khriachtchev, Jan Lundell, and Markku Rasanen
2.1 Introduction 15
2.2 Nature of Bonding 16
2.3 Computational Properties of HNgY 17
2.3.1 Molecular Structure 17
2.3.2 Stability 21
2.4 Preparative Methods 21
2.5 Spectroscopic Properties 23
2.5.1 Experimental Spectroscopic Observations 23
2.5.2 Computational Vibrational Spectra of HNgY 24
2.6 Selected Examples of HNgY Compounds 25
2.6.1 Xenon Compounds 25
2.6.2 Compounds of Lighter Noble Gases 26
2.7 HNgY Complexes 27
2.8 Reactions of HNgY Molecules with Hydrogen Atoms 29
2.9 Future Directions 31
References 32
3 Polycationic Clusters of the Heavier Group 15 and 16 Elements 35
Johannes Beck
3.1 Introduction 35
3.2 Principles of Stability for Polycationic Clusters 36
3.3 Synthetic Routes to Polyatomic Cations 37
3.4 Homopolyatomic Cations of the Chalcogens 39
3.4.1 Square-Planar Cations E42+ 39
3.4.2 Prism-Shaped Cations Te64+ and Te62+ 40
3.4.3 Eight-Atomic Molecular Ions E82+ and Te84+ 41
3.4.4 Towards Larger Clusters - Chalcogen Polycations with More than Eight Atoms 42
3.5 Homopolyatomic Cations of Bismuth 42
3.6 Heteronuclear Polycationic Clusters of the Heavier Group 15 and 16 Elements 44
3.7 Interactions Between Polycationic Clusters -From Weak Association to One-Dimensional Polymers 46
3.8 Summary and Outlook 49
References 50
4 Metal-Catalyzed Dehydrocoupling Routes to Rings, Chains, and Macromolecules based on Elements from Groups 13 and 15 53
Cory A. Jaska and Ian Manners
4.1 Introduction 53
4.2 Thermal Dehydrocoupling of Phosphine-Borane Adducts 54
4.3 Catalytic Dehydrocoupling of Secondary Phosphine-Borane Adducts 54
4.4 Catalytic Dehydrocoupling of Primary Phosphine-Borane Adducts 56
4.5 Thermal Dehydrocoupling of Amine-Borane Adducts 57
4.6 Catalytic Dehydrocoupling of Secondary Amine-Borane Adducts 58
4.7 Catalytic Dehydrocoupling of Primary Amine-Borane Adducts and NH3*BH3 59
4.8 Mechanism of Catalytic Dehydrocoupling of Amine-Borane and Phosphine-Borane Adducts 60
4.9 Application of the Catalytic Dehydrocoupling of Amine-Borane Adducts 62
4.10 Summary 63
References 63
5 Chemistry with Poly- and Perfluorinated Alkoxyaluminates: Gas-Phase Cations in the Condensed Phase? 65
Ingo Krossing and Andreas Reisinger
5.1 Introduction 65
5.2 Available Starting Materials 66
5.3 Weakly Bound Lewis Acid-Base Complexes of the Ag+ Cation 67
5.3.1 Ag(S8) Complexes 68
5.3.2 Complexes with P4S3 69
5.3.3 Complexes with P4 70
5.3.4 Complexes with C2H4 72
5.3.5 Anion Effects 73
5.4 Highly Electrophilic Cations 74
5.4.1 Binary Phosphorus-Halogen Cations 74
5.4.2 Simple Carbenium Ions 78
5.5 A Rationalization of the Special Properties of Salts of WCAs Based on Thermodynamic Considerations 80
5.5.1 Stabilization of Weakly Bound Complexes 81
5.5.2 Relative Anion Stabilities Based on Thermodynamic Considerations 82
5.6 Conclusions and Outlook 84
References 85
6 Aluminum(I) Chemistry 89
Herbert W. Roesky
6.1 Introduction 89
6.2 Preparation of Aluminum(I) Halides 89
6.3 Reactions of Aluminum(I) Halides 90
6.4 Chemistry of (Cp*Al)4 (8) 96
6.5 Reactions of [HC(CMeNAr)2]Al (17)
- Ar=2,6-i-Pr2C6H3 98
6.6 Conclusions 101
References 101
7 Divalent Scandium 105
Gerd Meyer, Liesbet Jongen, Anja-Verena Mudring, and Angela Moeller
7.1 Introduction 105
7.2 Synthesis 106
7.3 Scandium Diiodide, ScxI2 106
7.4 Other Scandium Dihalides? 110
7.5 The Ternary Scandium Halides AScxX3 (A=Alkali Metal, X=Cl, Br, I) 110
7.6 Conclusions 118
References 119
8 Rare-Earth Metal-Rich Tellurides - A Spectrum of Solid-State Chemistry, Metal-Metal Bonding, and Principles 121
John D. Corbett
8.1 Introduction 121
8.2 Novel Binary Tellurides 124
8.3 The Conceptual Polymerization of Sc2Te by Transition Metals 130
8.4 Versatility of the Fe2P-Type Structure and Some Amazing Substitutions 132
8.5 Diverse, Contrasting, and Yet Related Cluster Chain Motifs 136
References 141
9 Zintl Phases of Tetrelides - Old Problems and Their Solution 143
Reinhard Nesper
9.1 Introduction and Concept 143
9.2 Li13Si4 - One-Dimensional Metallicity vs. Cage Orbitals 144
9.3 Li13Si4 vs. Li13Ge4 Structure Type 149
9.4 Li12Si7 - Revisited 150
9.5 The Lanthanide Disilicide Problem 157
9.6 YbSi1.4 - A Beautiful Solution to a "Disorder Problem" 161
References 165
10 Nonclassical Sb-Sb Bonding in Transition Metal Antimonides 167
Holger Kleinke
10.1 Introduction: Violations of the Lewis Octet Rule? 167
10.2 Sb-Sb Interactions in Zintl Phases 170
10.2.1 General Remarks about Zintl Phases 170
10.2.2 Molecular Antimony Units in Zintl Phases 171
10.2.3 Extended Antimony Units in Zintl Phases 172
10.2.4 Beyond Classical Sb-Sb Single Bonds in Zintl Phases 173
10.3 Antimony Atom Substructures in Transition Metal Antimonides 177
10.3.1 Valence-Electron-Rich Transition Metal Antimonides 177
10.3.2 Valence-Electron-Poor Transition Metal Antimonides 180
10.4 Concluding Remarks 187
References 188
11 Transition Metal Organosulfur Coordination Polymers 193
Maochun Hong, Rong Cao, Weiping Su, and Xintiao Wu
11.1 Introduction 193
11.2 Chain-Like Polymers of Silver with Metal-Metal Interactions 194
11.3 Lamellar Polymers with Thiolato Bridges 197
11.4 Organosulfur Coordination Polymers with Tubular Structures 202
11.5 Conclusions 205
References 205
12 Molybdenum(Tungsten)-Copper(Silver) Thiolates: Rationally Designed Syntheses from "Reactive" Building Blocks 207
Ling Chen and Xin-Tao Wu
12.1 Introduction 207
12.2 One-Dimensional Thiometalate Polymers 209
12.2.1 Linear Chains 209
12.2.2 Wave-Like Chains 211
12.2.3 Zigzag Chains 211
12.2.4 Helical Chains 212
12.2.5 One-Dimensional Chains with Square Units 212
12.2.6 Double Chains 213
12.2.7 Hanging Ladder Chains 213
12.2.8 Semiconductivity and Theoretical Calculations 214
12.3 Cage-Like Clusters 215
12.4 Conclusions 217
References 218
13 Reactivity of Unsaturated Organic Compounds at Ruthenium(II) Centers - The Relevance of Metallacyclopentatriene Intermediates 221
Roland Schmid and Karl Kirchner
13.1 Introduction 221
13.2 The Cyclotrimerization of Alkynes Mediated by the Cp'RuCl Fragment 223
13.3 The Cyclocotrimerization of Alkynes with Unsaturated Organic Molecules Mediated by the Cp'RuCl Fragment 227
13.4 Dramatic Changes Seen Upon Replacement of Cl in Cp'RuCl with ER3 (E=P, As, Sb) or CO 228
13.5 What Happens if the Phosphine Ligand is Tethered? 235
13.6 Outlook 238
References 239
14 Osmium(VIII) Oxide and Oxide Fluoride Chemistry 243
Michael Gerken and Gary J. Schrobilgen
14.1 Introduction: Oxidation State +8 243
14.2 Osmium Tetroxide and Perosmates 243
14.2.1 Osmium Tetroxide Adducts 245
14.3 Nitrido Osmates and Organo-Imido Osmates 249
14.4 Osmium Oxide Fluoride Chemistry 249
14.4.1 Osmium Trioxide Difluoride 250
14.4.2 Osmium Dioxide Tetrafluoride 255
14.4.3 The trans Influence 259
14.4.4 Computational Results and Bonding 261
14.4.5 NMR Spectroscopy 262
14.5 Outlook 262
References 264
15 Liquid-Crystalline Lanthanide Complexes 267
Koen Binnemans
15.1 Introduction 267
15.2 Mesophases 268
15.3 Lanthanide Complexes with Schiff's Base Ligands 271
15.4 Complexes of _-Diketonates 275
15.5 Bis(benzimidazolyl)pyridines 277
15.6 Mixed f-d Metallomesogens 279
15.7 Phthalocyanines 280
15.8 Porphyrins 281
15.9 Crown Ether Complexes 283
15.10 Magnetic Anisotropy and Alignment in a Magnetic Field 284
15.11 Luminescent Liquid Crystals 287
15.12 Conclusions 289
References 289
16 Rare-Earth Borates: An Overview from the Structural Chemistry Viewpoint 293
Jianhua Lin, Y. X. Wang, and L.Y. Li
16.1 Introduction 293
16.2 Rare-Earth Oxyborates 294
16.3 Rare-Earth Orthoborates 296
16.3.1 Aragonite and Calcite-Type Orthoborates 296
16.3.2 Vaterite-Type Orthoborates 297
16.4 Anhydrous Rare-Earth Polyborates 304
16.4.1 Ln4B6O15 305
16.4.2 Ln2B4O9 305
16.4.3 Rare-Earth Metaborates 307
16.4.4 Rare-Earth Pentaborates 307
16.5 Hydrated Rare Earth Polyborates 311
16.6 Conclusions and Further Studies 315
References 316
17 Ordered Siliceous Mesostructured Materials: Synthesis and Morphology Control 319
Pegie Cool, E. F. Vansant, and O. Collart
17.1 Introduction 319
17.2 Mesoporous Siliceous Materials: State-of-the-Art 320
17.2.1 Mesoporous Structures 320
17.2.1.1 Hexagonal Mesoporous Structures MCM-41, SBA-15 322
17.2.1.2 Cubic Mesoporous Structure MCM-48 323
17.2.2 Synthesis of Siliceous Mesoporous Materials 323
17.2.2.1 Key Steps in the Synthesis 329
17.2.2.2 Key Parameters in the Syntheses: Structure-Directing Agents 330
17.3 Case Study: Control of the Morphology and the Structural Ordering of MCM Materials by the Addition of Alcohols 334
17.3.1 Structure Determination 334
17.3.2 Effect of the Alcohol Concentration 339
17.4 Conclusions 344
References 344
18 Local Crystal Chemistry, Structured Diffuse Scattering, and Inherently Flexible Framework Structures 347
Ray L. Withers and Yun Liu
18.1 Introduction 347
18.2 Recent Methodological Developments 349
18.3 Applications 352
18.3.1 Microporous Molecular Sieve Materials 352
18.3.2 The A2BM2O8 (A=Sr, Ba
- B=Ti, V
- M=Si, Ge, . . .) Family of Layered Fresnoites 354
18.3.3 The Silica Polymorphs 357
18.4 Future Directions and Conclusions 360
References 361
19 Non-Oxide Optical Glasses: Properties, Structures, and Applications 365
Bruno Bureau and Jean Luc Adam
19.1 Introduction 365
19.2 Glass Compositions and Properties 365
19.2.1 Fluoride Glasses 365
19.2.2 Chalcogenide Glasses 368
19.3 Structural Aspects 370
19.3.1 Fluoride Glasses 370
19.3.1.1 Fluorozirconate Glass: ZBLAN 370
19.3.1.2 Transition Metal Fluoride Glasses: PZG 370
19.3.2 Chalcogenide Glasses 374
19.4 Optical Properties and Applications 377
19.4.1 Fiber Lasers 377
19.4.2 Optical Amplifiers 380
19.4.3 Lenses for Infrared Cameras 382
19.4.4 Optical Sensors 384
19.4.4.1 Optical Fibers 384
19.4.4.2 Principle and Design 384
19.4.4.3 Application in the Environment, Biology, and Medicine 386
References 389
Index 393
- 巻冊次
-
3 ISBN 9783527315109
内容説明
Metal clusters are on the brink between molecules and nanoparticles in size. With molecular, nano-scale, metallic as well as non-metallic aspects, metal clusters are a growing, interdisciplinary field with numerous potential applications in chemistry, catalysis, materials and nanotechnology.
This third volume in the series of hot topics from inorganic chemistry covers all recent developments in the field of metal clusters, with some 20 contributions providing an in-depth view. The result is a unique perspective, illustrating all facets of this interdisciplinary area:
* Inter-electron Repulsion and Irregularities in the Chemistry of Transition Series
* Stereochemical Activity of Lone Pairs in Heavier Main Group Element Compounds
* How Close to Close Packing?
* Forty-Five Years of Praseodymium Diiodide
* Centered Zirconium Clusters
* Titanium Niobium Oxychlorides
* Trinuclear Molybdenum and Tungsten Cluster Chalcogenides
* Current State of (B,C,N)-Compounds of Calcium and Lanthanum
* Ternary Phases of Lithium with Main-Group and Late-Transition Metals
* Polar Intermetallics and Zintl Phases along the Zintl Border
* Rare Earth Zintl Phases
* Structure-Property Relationships in Intermetallics
* Ternary and Quaternary Niobium Arsenide Zintl Phases
* The Building Block Approach to Understanding Main-Group-Metal Complex Structures
* Cation-Deficient Quaternary Thiospinels
* A New Class of Hybrid Materials via Salt Inclusion Synthesis
* Layered Perrhenate and Vanadate Hybrid Solids
* Hydrogen Bonding in Metal Halides
* Syntheses and Catalytic Properties of Titanium Nitride Nanoparticles
* Solventless Thermolysis
* New Potential Scintillation Materials in Borophosphate Systems.
With its didactical emphasis, this volume addresses a wide readership, such that both students and specialists will profit from the expert contributions.
目次
Inter-Electron Repulsion and Irregularities in the Chemistry of Transition Series
Stereochemical Activity of Lone Pairs in Heavier Main Group Element Compounds
How Close to Close Packing?
Forty-Five Years of Praseodymium Diiodide, PrI2
Centered Zirconium Clusters: Mixed-Halide Systems
Titanium Niobium Oxychlorides: Ligand Combination Strategy for the Preparation of Low-Dimensional Metal Cluster Materials
Trinuclear Molybdenum and Tungsten Cluster Chalcogenides: From Solid State to Molecular Materials
Current State of (B,C,N)-Compounds of Calcium and Lanthanum
Compositional, Structural and Bonding Variations in Ternary Phases of Lithium with Main-Group and Late-Transition Metals
Polar Intermetallics and Zintl Phases along the Zintl Border
Rare Earth Zintl Phases: Novel Magnetic and Electronic Properties
Understanding of Structure-Forming Factors and Theory-Guided Exploration of Structure-Property Relationschips in Intermetallics
Ternary and Quaternary Niobium Arsenide Zintl Phases
The Building Block Approach to Understanding Main-Group-Metal Complex Structures -
More than just "Attempting to Hew Blocks with a Razor"
Cation-Deficient Quaternary Thiospinels
A New Class of Hybrid Materials via Salt Inclusion Synthesis
Layered Perrhenate and Vanadate Hybrid Solids: On the Utility of Structural Relationships
Hydrogen Bonding in Metal Halides: Lattice Effects and Electronic Distortions
Syntheses and Catalytic Properties of Titanium Nitride Nanoparticles
Solventless Thermolysis: A Possible Bridge Between Crystal Structure and Nano Synthesis?
New Potential Scintillation Materials in Borophosphate Systems
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