Cover image for Inorganic chemistry highlights
Title:
Inorganic chemistry highlights
Author:
Meyer, Gerd.
Publication Information:
Weinheim : Wiley-VCH, [2002]

©2002
Physical Description:
xv, 324 pages : illustrations ; 25 cm
Language:
English
Contents:
Molten zintl alloys -- Structure and bonding around the zintl border -- Structure prediction and determination of crystalline compounds -- Multivalent cation conductors -- The potential of pentagonal building blocks : from giant ring-shaped to spherical polyoxometalate clusters -- Molybdenum peroxo complexes as catalysts in olefin epoxidation -- Syntheses of rare earth organometallics, organoamides, and aryloxides from the metals -- Enzyme structures : active site structural and functional aspects of purple acid phosphatase and catechol oxidase -- Aminotroponimainates as ligands for group 3 and lanthanide complexes : coordination chemistry and catalysis -- Metalla-calix[4]arenes : how they assist the transformations of hydrocarbons into metalla-alkylidenes, of dinitrogen into metalla-nitrides, and of carbon monoxide into metalla-carbides -- Metal carbonyl cations and their derivatives : a new class of superelectrophiles -- Borylene complexes -- Silaboranes -- Carbaalanes : a new class of compounds containing clusters of aluminum and carbon atoms -- Molecular aluminium and gallium subhalides -- Recent developments in the chemistry of covalent main group azides -- Silacalix-[n]-phosphinines : sp²-phosphorus equivalents of CO matrices -- Using dinitrogen as a raw material : is there a future? -- Organoxenon compounds.
Subject Term:
Electronic Access:
Table of contents http://www.loc.gov/catdir/toc/wiley023/2002523652.html
ISBN:
9783527302659
Format :
Book

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Summary

Summary

Although research is becoming increasingly specialized these days, which also holds for Inorganic Chemistry, "Inorganic Chemistry Highlights" intend to give an overview on new developments in selected areas of this discipline.

Scientists from all over the world present current and widely interesting contributions highlighting their research in
- molecular chemistry
- main group chemistry
- solid state chemistry
- coordination chemistry
- materials science
- bioinorganic chemistry
- related topics

The book is addressed to everyone looking out for an insight in the inorganic world beyond the own special research area.


Author Notes

Gerd Meyer and Dieter Naumann are the authors of Inorganic Chemistry Highlights, published by Wiley.


Table of Contents

Willem van der Lugt and Peter VerkerkGordon J. Miller and Chi-Shen Lee and Wonyoung ChoeJ. Christian Schon and Martin JansenGin-ya Adachi and Nobuhito ImanakaLeroy CroninWerner R. ThielGlen B. Deacon and Craig M. ForsythAnnette Rompel and Carsten Gerdemann and Andreas Vogel and Bernt KrebsPeter W. RoeskyCarlo FlorianiHelge Willner and Friedhelm AubkeHolger BraunschweigLars WesemannWerner UhlHansgeorg Schnockel and Christoph KlempWolfgang Fraenk and Thomas M. KlapotkeNicolas Mezailles and Francois Mathey and Pascal Le FlochSandro GambarottaWieland Tyrra and Dieter Naumann
1 Molten Zintl Alloysp. 1
1.1 Introduction and some Terminologyp. 1
1.2 The Gradual Development of Stoichiometry in Non-Clustering Liquid Ionic Alloysp. 2
1.3 Physical Properties and Detection of Liquid Zintl Compoundsp. 3
1.4 Neutron Diffraction Measurements and their Analysis: Introductionp. 7
1.5 Neutron Diffraction; Zintl-Klemm Alloysp. 8
1.6 Zintl-Klemm Alloys: Theoretical Contributionsp. 11
1.7 Structures of Alkali-Tl And Alkali-Ga Alloysp. 12
1.8 Conclusions and Final Remarksp. 15
2 Structure and Bonding Around the Zintl Borderp. 21
2.1 Introductionp. 21
2.2 Metals versus Nonmetals: Physical and Chemical Principlesp. 23
2.3 Elements at the Zintl Borderp. 26
2.4 Electron-counting Rulesp. 28
2.5 New Complex Compounds at the Zintl Borderp. 35
2.5.1 Left of the Zintl Border: From Hume-Rothery to Zintlp. 35
2.5.2 Right of the Zintl Border: Unsaturated Bonding and Internal Redox Processesp. 43
2.6 Future Directions and Summaryp. 50
3 Structure Prediction and Determination of Crystalline Compoundsp. 55
3.1 Introductionp. 55
3.2 General Approach to Structure Predictionp. 56
3.2.1 Fundamentalsp. 56
3.2.2 Modular Approachp. 57
3.2.3 Examplesp. 58
3.3 Investigations of Restricted Landscapesp. 61
3.3.1 Alternative Methods for Generation of Candidate Structuresp. 61
3.3.2 Molecular Crystalsp. 62
3.4 Structure Determinationp. 65
3.4.1 Restricted Exploration of the Energy Landscapep. 66
3.4.2 Combined Optimizationp. 67
3.5 Concluding Remarksp. 68
4 Multivalent Cation Conductorsp. 71
4.1 Introductionp. 71
4.2 Divalent Cation Conductorsp. 72
4.2.1 [beta]-Alumina-type Structurep. 72
4.2.2 M[superscript 2+]Zr[subscript 4](PO[subscript 4])[subscript 6]p. 76
4.2.3 YPO[subscript 4]-based Compoundsp. 84
4.3 Trivalent Ion Conductorsp. 85
4.3.1 Trivalent Cation Conductors with [beta]-Al[subscript 2]O[subscript 3]-Type Structuresp. 85
4.3.2 [beta]-Al[subscript 2]O[subscript 3]-related Phasesp. 89
4.3.3 [beta]-LaNb[subscript 3]O[subscript 9]p. 90
4.3.4 Sc[subscript 2](WO[subscript 4])[subscript 3]-Type Structuresp. 92
4.3.5 Phosphate-Based Trivalent Cation Conductorsp. 104
4.4 Tetravalent Cation Conductorsp. 106
4.4.1 Silicon Nitridep. 107
4.4.2 Phosphate-Based Tetravalent Cation Conductorsp. 107
4.5 Conclusionsp. 109
5 The Potential of Pentagonal Building Blocks: From Giant Ring-shaped to Spherical Polyoxometalate Clustersp. 113
6 Molybdenum Peroxo Complexes as Catalysts in Olefin Epoxidationp. 123
6.1 Introductionp. 123
6.2 Mechanistic Fundamentalsp. 126
6.3 Pyrazolylpyridine Complexesp. 127
6.3.1 Mechanistic Investigationsp. 128
6.3.2 Structure/Activity Relationshipsp. 131
6.3.3 Ligand Fluxionalityp. 133
7 Syntheses of Rare Earth Organometallics, Organoamides, and Aryloxides from the Metalsp. 139
7.1 Introductionp. 139
7.2 Metal-based Synthesesp. 140
7.2.1 Redox Transmetalation with Mercury Reagentsp. 140
7.2.2 Redox Transmetalation with Thallium(I) Reagentsp. 142
7.2.3 Redox Transmetalation/Ligand-Exchangep. 144
7.2.4 Synthesis of Lanthanoid Trichloridesp. 146
7.2.5 The Direct Reaction of Rare Earth Metals with Weak Protic Reagents at Elevated Temperaturesp. 147
7.3 Conclusionsp. 151
8 Enzyme Structures: Active Site Structural and Functional Aspects of Purple Acid Phosphatase and Catechol Oxidasep. 155
8.1 Introduction: Aim and Purpose of Bioinorganic Chemistryp. 155
8.2 Purple Acid Phosphatasesp. 155
8.2.1 The Crystal Structure of a Plant Purple Acid Phosphatase (kbPAP) Containing a Dinuclear Iron-Zinc Centerp. 156
8.2.2 Comparison of Mammalian and Plant PAP Structurep. 158
8.2.3 Reaction Mechanismp. 159
8.2.4 Physiological Rolep. 160
8.3 Catechol Oxidasep. 160
8.3.1 The Crystal Structure of a Plant CO (ibCO) containing a Dinuclear Copper Centerp. 161
8.3.2 Comparison of the CO Structure with Different HC Structuresp. 163
8.3.3 Reaction Mechanismp. 164
8.3.4 Physiological Rolep. 166
9.1 Introductionp. 171
9 Aminotroponiminates as Ligands for Group 3 and Lanthanide Complexes--Coordination Chemistry and Catalysisp. 171
9.2 Ligand Synthesisp. 172
9.3 Metal Complexesp. 173
9.3.1 Complexes of N,N'-Disubstituted Aminotroponiminatesp. 173
9.3.2 Complexes of Mono-bridged Bis-aminotroponiminatesp. 176
9.4 Summaryp. 179
10 Metalla-calix[4]arenes: How they Assist the Transformations of Hydrocarbons into Metalla-alkylidenes, of Dinitrogen into Metalla-nitrides, and of Carbon Monoxide into Metalla-carbidesp. 181
10.1 Topic of this Chapterp. 181
10.2 Introductionp. 181
10.3 The Synthesis and the Chemistry of Metal-alkylidene and Metalalkylidyne Functionalitiesp. 183
10.4 Reductive Cleavage of Dinitrogen to Nitrides, and of Carbon Monoxide to Carbidesp. 188
11 Metal Carbonyl Cations and Their Derivatives--A New Class of Superelectrophilesp. 195
12 Borylene Complexesp. 213
12.1 Introductionp. 213
12.2 Bridged Borylene Complexesp. 213
12.3 Terminal Borylene Complexesp. 216
13 Silaboranesp. 219
14 Carbaalanes--A New Class of Compounds Containing Clusters of Aluminium and Carbon Atomsp. 229
14.1 Introductionp. 229
14.2 Synthesis of Carbaalanesp. 230
14.3 Structuresp. 233
14.4 Spectroscopic Findingsp. 237
14.5 Quantum-chemical Calculationsp. 239
14.6 Chemical Reactivityp. 240
14.7 Concluding Remarksp. 242
15 Molecular Aluminium and Gallium Subhalidesp. 245
15.1 Introductionp. 245
15.2 Synthesisp. 246
15.3 Productsp. 247
15.3.1 [MX subscript n] Speciesp. 247
15.3.2 M[subscript 2]X[subscript 4] Speciesp. 248
15.3.3 M[subscript 3]X[subscript 5] Speciesp. 250
15.3.4 M[subscript 4]X[subscript 6] Speciesp. 251
15.3.5 M[subscript 5]X[subscript 7] Speciesp. 251
15.3.6 Al[subscript 22]Br[subscript 20] and Al[subscript 14]I[subscript 6]R[subscript 6 superscript 2-] Speciesp. 254
15.4 Conclusionp. 255
16 Recent Developments in the Chemistry of Covalent Main Group Azidesp. 259
16.1 Introductionp. 259
16.2 Group 13 Azidesp. 259
16.2.1 Boron Azidesp. 259
16.2.2 Aluminium, Gallium, and Indium Azidesp. 265
16.3 Group 14 Azidesp. 267
16.3.1 Carbon Azidesp. 267
16.3.2 Germanium Azidesp. 268
16.4 Group 15 Azidesp. 271
16.4.1 The N[superscript + subscript 5] Cation and Hydrogen Diazidep. 271
16.4.2 Arsenic Azidesp. 272
16.4.3 Antimony and Bismuth Azidesp. 273
16.5 Group 16 Azidesp. 273
16.5.1 The Reaction between OF[subscript 2] and CsN[subscript 3]p. 273
16.5.2 Tellurium Azidesp. 275
16.6 Group 17 Azidesp. 275
16.7 Updatep. 276
17 Silacalix-[n]-phosphinines: sp[superscript 2]-Phosphorus Equivalents of CO Matricesp. 279
18 Using Dinitrogen as a Raw Material: Is there a Future?p. 285
18.1 Introductionp. 285
18.2 Formation of NH[subscript 3]p. 285
18.3 N[subscript 2] Reductionp. 287
18.4 Catalysisp. 288
18.5 Cooperative N[subscript 2] Reductionp. 290
18.6 Conclusionp. 293
19 Organoxenon Compoundsp. 297
19.1 Introductionp. 297
19.2 Evidence for Xenon--Carbon Compoundsp. 298
19.3 Synthetic Methods for the Preparation of Organoxenon(II) Compoundsp. 299
19.3.1 Preparation of Organoxenon(II) Fluoroborates from Organoboranes and Xenon Difluoridep. 299
19.3.2 Synthesis of Arylxenon(II) Trifluoromethanesulfonates through Electrophilic Aromatic Substitution Reactionsp. 301
19.3.3 Direct Access to Xe(C[subscript 6]F[subscript 5])[subscript 2]p. 304
19.3.4 Ligand Exchange Reactions of Fluorophenylxenon Compoundsp. 306
19.3.5 Synthesis of Alkenylxenon Derivatives by Fluorination of Arylxenon Compoundsp. 307
19.3.6 Xenon(IV)-Carbon Compoundsp. 308
19.4 Crystallographic and Spectroscopic Characteristics of Organoxenon Compoundsp. 309
19.4.1 Crystallographic Datap. 309
19.4.2 NMR Spectrap. 311
19.4.3 Vibrational Spectrap. 311
19.4.4 Mass Spectrap. 311
19.5 Reactions of Organoxenon Compoundsp. 312
Indexp. 317