Inorganic Reactions and Methods, The Formation of Bonds to O, S, Se, Te, Po (Part 2)

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ISBN: 9780471246770 | 0471246778
Cover: Hardcover
Copyright: 10/15/1998

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Boasting numerous industrial applications, inorganic chemistry forms the basis for research into new materials and bioinorganic compounds such as calcium that act as biological catalysts. Now complete, this highly acclaimed series presents current knowledge in all areas of inorganic chemistry, including chemistry of the elements; organometallic, polymeric and solid-state materials; and compounds relevant to bioinorganic chemistry.

How to use this Book

xvii

Preface to the Series

xxiii

Editorial Consultants to the Series

xxvii

Contributors to Volume 6

xxix

Formation of the Group VIB (O, S, Se, Te, Po)---Group IB (Cu, Ag, Au) or IIB (Zn, Cd, Hg) Metal Bond

(53)

Introduction

(1)

Formation of the Oxygen-Group IB or IIB Bond

(13)

From Dioxygen and Ozone

(1)

By Reaction with the Metal

(1)

By Addition to Low-Valent and Unsaturated Metal Complexes

(1)

By Insertion into Metal---Ligand Bonds

(1)

From Water and Alcohols

(1)

By Reaction with Elements

(1)

By Hydrolysis or Alcoholysis of Metal---Ligand Bonds

(2)

From Hydrogen Peroxide and Organic Peroxides

(1)

By Oxidation of the Metals and Their Complexes

(1)

By Oxidation of the Ligands Coordinated to the Metals

(1)

From Neutral Oxygen Donor Ligands [Ethers, Aldehydes, Ketones, Pyridine N-Oxides, Phosphine Oxides, Arsine Oxides and Dialkyl(aryl) Sulfoxides]

(1)

By Ligand Displacement Reactions with Transition Metal Complexes

(1)

By Insertion into the Metal---Ligand Bonds

(1)

From Bidentate and Polydentate Oxygen Donor Ligands (from Polyethers and Crown Ethers, Macrocycles, 2,4-Pentanedione, etc.)

(1)

From Oxides of the Main Group Elements

(1)

By Reaction with the Metals

(1)

By Reaction with Complexes of the Metals

(1)

By Insertion into Metal---Ligand Bonds

(1)

From OH-, OR-, O2/2, O-2

(1)

By Ligand Substitution Reactions with Complexes of the Metals

(1)

By Oxidation of the Metals and Their Complexes

(1)

By Metal Atom and Related Reactions

(2)

Formation of the Bond Between Sulfur and a Group IB or IIB Element

(14)

From Sulfur

(1)

By Direct Reaction with Metals

(1)

By Reaction with Metal Complexes

(1)

From Hydrogen Sulfide, Hydrogen Polysulfides, and Thiols

(3)

From Thiocarbonyls, Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands

(1)

From Organic Thio Acids and Other Thio Acids of Main Group Elements

(1)

By Oxidation of the Metals or Their Complexes

(1)

By Ligand Replacement Reactions with Complexes of the Metals and by Sulfur Atom Abstraction

(1)

From Bidentate and Polydentate Sulfur Donor Atoms

(1)

By Sulfur Addition, Oxidation and Sulfur Abstraction Reactions

(1)

By Ligand Substitution Reactions

(1)

From Sulfur Containing Anions (S2-, S2x-, [HS-], [RS]-)

(6)

By Metal Atom and Related Reactions

(1)

Formation of the Bond Between Selenium, Tellurium, and Polonium and Group IB or IIB Elements

(26)

By Reactions with the Group IB and IIB Metals

(1)

Formation of the Bond with Selenium

(2)

Formation of the Bond with Tellurium

(2)

Electrolytic Reactions Between the Elements

(1)

By Reaction with Group IB or Group IIB Metal Compounds

(1)

Binary Compounds

(1)

Ternary Compounds

(1)

By Reactions of Binary Acids of Selenium and Tellurium and Their Derivatives with Metal Compounds

(2)

By Reaction of Oxides of Selenium and Tellurium with Metal Compounds

(1)

By Reactions of the Anions and Oxyanions of the Elements with Metal Compounds

(2)

From Donor Ligands Incorporating the Elements Selenium and Tellurium

(1)

By Reaction with the Metals

(1)

Chemically Driven Reactions

(1)

Electrochemically Driven Reactions

(1)

By Reactions with Metal Compounds

(1)

Reaction with Alkali Metal Selenides, Polyselenides, Tellurides, and Polytellurides

(2)

Reaction with Organochalcogenides

(1)

Reaction with Organoselenols and Tellurols

(1)

Reaction with Trimethylsilyl Chalcogenides

(1)

Reaction with Dialkylselenocarbamates

(1)

Reaction with Triphenylphosphine Chalcogenides

(1)

Reaction with Selenocyanate and Selenourea

(2)

Reaction with Tetrahydroselenophene and Tetrahydrotellurophene and Derivatives

(1)

Reaction with Miscellaneous Ligands

(1)

By Reaction with Selenium or Tellurium Compounds in Metal---Organic Chemical Vapor Deposition (MOCVD) and Related Reactions

(4)

Formation of Bonds Between the Group VIB (O, S, Se, Te, Po) Elements and Transition and Inner Transition Metals

(70)

Introduction

(1)

Formation of the Oxygen- Transition Metal and Oxygen-Inner Transition Metal Bond

(30)

From Dioxygen and Ozone

(1)

By Reaction with the Transition or Inner Transition Metal

(1)

By Addition to Low-Valent and Unsaturated Metal Complexes

(3)

By Insertion into Metal---Ligand Bonds

(5)

From Water

(1)

By Substitution of Transition and Inner Transition Metal Ligand Bonds

(1)

By Hydrolysis of Transition and Inner Transition Metal---Ligand Bonds

(1)

From Hydrogen Peroxide

(1)

By Oxidation of Transition and Inner Transition Metal Elements and Their Complexes

(1)

By Oxidation of a Ligand Coordinated to a Transition and Inner Transition Metal Complex (Insertion Reaction)

(1)

By Homolytic Transition and Inner Transition Metal---Ligand Substitution Reactions

(1)

From Alcohols and Phenols

(1)

By Substitution of Transition and Inner Transition Metal---Ligand Bonds

(1)

By Alcoholysis of Transition and Inner Transition Metal---Ligand Bonds

(2)

By Oxidation of Transition and Inner Transition Metal---Ligand Bonds

(1)

From Organic Peroxides

(1)

By Oxidation of Transition and Inner Transition Metal---Ligand Bonds

(1)

By Substitution Reactions of Transition and Inner Transition Metal---Ligand Bonds

(1)

By Reaction with a Ligand Coordinated to Transition and Inner Transition Metal Elements

(1)

From Neutral Oxygen Donor Ligands (R2CO, R2SO, R3PO, R3AsO, etc)

(1)

By Ligand Substitution Reactions with Transition and Inner Transition Metal Complexes

(2)

By Insertion into Transition and Inner Transition Metal---Ligand Bonds: R1R2CO

(1)

By Oxidation of the Transition and Inner Transition Metal Complexes (Ligand Degradiation, Oxygen Abstraction)

(1)

From Bidentate and Polydentate Oxygen Donor Ligands (Crown Ethers, Macrocycles, 2,4-Pentanedione, etc.)

(1)

By Substitution of Transition and Inner Transition Metal---Ligand Bonds

(2)

By Oxidation of Transition and Inner Transition Metal Complexes

(1)

From Main Group Element Oxides

(1)

By Direct Addition to the Transition and Inner Transition Metals and Their Complexes

(1)

By Insertion into Transition and Inner Transition Metal Bonds

(1)

By Oxidation of Transition and Inner Transition Metals and Their Compounds

(2)

From OH-, O2-, O2-, and O2/2

(1)

By Ligand Substitution Reactions with Transition and Inner Transition Metal Complexes

(1)

By Oxidation of the Transition and Inner Transition Metals and Their Complexes

(1)

From Alkoxide and Carboxylate Anions

(1)

By Substitution of Transition and Inner Transition Metal---Ligand Bonds

(3)

From Metal Atom and Related Reactions

(1)

Abstraction and Electron Transfer Processes

(1)

Oxidative Addition/Complexation Reactions

(1)

Simple Orbital Mixing: Dioxygen and Carbon Dioxide with Metal Atoms

(1)

Formation of the Sulfur-Transition and Inner-Transition Metal Bond

(40)

From Sulfur

(1)

By Reaction with the Transition and Inner Transition Metal

(1)

By Reaction with Transition Metal and Inner Transition Metal Compounds

(1)

From Hydrogen Sulfide, Polysulfides, and Thiols

(1)

By Substitution Reactions with Transition Metal and Inner Transition Metal Compounds

(3)

By Insertion of Sulfur into Transition and Inner Transition Metal---Ligand Bonds

(1)

By Oxidation of the Transition Metal and Inner Transition Metal Complexes

(1)

From Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands

(1)

From Organic Thioacids, Thiophosphates, Xanthates, and Other 1,1-Dithio Compounds

(1)

By Oxidation of the Metals and Their Complexes

(1)

By Ligand Replacement Reactions with Complexes of the Metals

(4)

By Insertion of CS2 (or P4S10) into Metal---Ligand Bonds

(1)

From Bidentate (excluding 1,1-dithiols) and Polydentate Sulfur Donor Ligands

(1)

By Sulfur Addition, Oxidation, and Sulfur Abstraction Reactions

(1)

By Ligand Substitution Reactions

(1)

From Sulfur Anions (S2-, HS-, S2x-, RS)-Transition and Inner Transition Metal Bonds

(1)

With Sulfur Anions (S2-, [HS-])

(7)

With Polysulfido Anions (S2x)

105

(4)

With Organosulfur Anions ([RS])

109

(6)

From Metal Atom and Related Reactions

115

(1)

Abstraction Processes

115

(1)

Oxidative Addition/Complexation Reactions

116

(1)

Formations of the Selenium-, Tellurium-, and Polonium- Transition and Inner Transition Metal Bond

116

(8)

Formation of the Bond Between Group VIB (O, S, Se, Te, Po) and Group O (Noble Gas) Elements

124

(6)

Introduction

124

(1)

By Reactions of Xenon Fluorides and Oxyfluorides with Oxides and Oxysalts

124

(3)

By Reaction of Xenon Fluorides and Oxyfluorides with Oxyacids and Their Derivatives

127

(2)

Bonds Between Oxygen and Krypton or Radon

129

(1)

Formation of Non-stoichiometric Oxides

130

(121)

Introduction

130

(27)

Basic Defect Equilibria: Thermodynamic and Structural Principles

130

(1)

Inherent Point Defect and Electron Band Equilibria

130

(2)

External Equilibrium with Oxygen Fugacity

132

(1)

Relations Between Nonstoichiometry and Physical Properties

133

(1)

Nonstoichiometry and Shear Planes

134

(1)

Introduction

134

(1)

Structural Properties

135

(2)

Stability

137

(4)

Extended Defects

141

(1)

Crystallographic Shear

141

(2)

Tunnel and Pentagonal Column Phases

143

(3)

Chemical Twinning and Related Structures

146

(3)

Coherent Intergrowth

149

(1)

Homologous Series Formed by Ordered Extended Defects

149

(1)

Disordered Extended Defects

150

(1)

Classification of Nonstoichiometric Oxides

151

(1)

Oxide Phases with Narrow Composition Ranges

152

(1)

Grossly Nonstoichiometric Phases

153

(1)

Homologous Series of Metal Oxides

154

(1)

Coherently Intergrown Structures

155

(1)

Oxides with Modulated Structures

155

(2)

Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper

157

(18)

Binary Oxides with Narrow Chemically Insignificant Composition Range

157

(1)

Binary Oxides with a Wide Composition Range

158

(1)

Transition Metal Lower Oxides, TiO, VO, MnO, FeO, CoO, NiO, NbO, and Cu2O

158

(2)

Oxygen-Deficient, Fluorite-Related Structures: Lanthanide Oxides (Ce, Pr, and Tb higher oxides)

160

(5)

Oxygen-Excess Fluorite Structures, UO2 +

165

(1)

Multiple Oxides with Point Defect and Defect Complex Equilibria

166

(1)

Doped Oxide Phases

166

(1)

Point Defect Nonstoichiometry in Spinels and Related Oxides

167

(3)

Wide-Range Nonstoichiometry: Perovskite-Derived Structures

170

(2)

Wide-Range Nonstoichiometry: Oxygen-Deficient Fluorite Structures

172

(1)

Wide-Range Nonstoichiometry: Mixed Cation Oxides. Induced Valence Effects by Substantial Substitution of Cations Having Different Valency

173

(2)

Operationally Nonstoichiometric Oxide Phases

175

(76)

Binary Oxides: Crystallographic Shear Structures

175

(1)

Rutile-Related Structures

175

(2)

ReO3-Related Structures: Molybdenum and Tungsten Oxides

177

(1)

Niobium Oxides and Related Structures

178

(4)

Nonstoichiometric Layer Structure Oxides

182

(1)

Layered Oxides Based on the Perovskite Structure

183

(1)

Intergrowth of Pervoskite with Rock Salt Layers --- Ruddlesden/Popper Phases

183

(1)

High Temperature Superconducting Cuprates

184

(7)

Intergrowth of Perovskite with ``Bi2O2'' Layers --- Aurivillius Phases

191

(1)

Brownmillerite Family (AMO3)n, AMO2

192

(1)

Titanates and Niobates, AnMnO3n + 2 and Molybdates, Cs2MonO3n + 1 Derived from the Perovskite Structure

193

(2)

Oxides Based on the Spinel Structure: Hexagonal Ferrites, β-Alumina Oxide Types, and LixM2O4 (M = Ti, V, Mn)

195

(1)

Hexagonal Ferrites

195

(1)

The β-Alumina Family

196

(1)

LixM2O4 (M = Ti, V, Mn) Phases

197

(1)

Intergrowths of the Cage Oxide A3M8O21 with a Tunnel Structure, A3M6Si4O26

197

(2)

Oxides with Intercalation Structures: Layers Built Up of Edge-Sharing Octahedra

199

(1)

Vanadium Bronzes

199

(3)

HxMoO3: Hydrogen-Intercalated Compounds of Molybdenum Trioxide

202

(1)

Molybdenum Bronzes AxMoyOz

203

(4)

AxMO2 Oxides

207

(3)

Another Family of AxMO2 Oxides (M = V, Cr, Mn, Co, Ni; A = Li, Na)

210

(1)

Titanates and Titanoniobates (or Tantalates) with a Layer Structure: Ion Exchange Properties

211

(3)

Tunnel Structure Oxides

214

(1)

Tungsten, Molybdenum Bronzes, and Related Structures

215

(7)

Titanium Bronzes and Related Oxides

222

(3)

Hollandite, Psilomelane, Ramsdellite, and Related Oxides

225

(3)

Vanadium Bronzes with a Three-Dimensional Structure

228

(1)

Complex Oxides with Host-Lattice Built up from Octahedra and Tetrahedra

228

(1)

Phosphate Tungsten Bronzes (PTB)

229

(4)

Phosphate Niobium Bronzes (PNB)

233

(4)

Phosphate Molybdenum Oxides

237

(2)

Other Reduced Transition Metal Phosphates

239

(1)

Siliconiobdates, Silicotantalates, and Corresponding Germanium Compounds

239

(1)

Adaptive Structures

240

(1)

Oxides with Vernier-Type Adaption Structures

241

(4)

Double Oxides Based on Tantalum Pentoxide and Related Phases

245

(4)

The Metal Uranates and Related Oxides

249

(1)

Mixed Valence, Mixed Anion Phases, Including Oxides with Cations of Variable Valence (or Mixed Cations) Balanced by Substitution of Altervalent Anions

250

(1)

Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides

251

(48)

Introduction

251

(1)

Chemical Bonding and Variation of Physical Properties by Means of Chemical Parameters

252

(3)

d-Transition Metal Chalconides

252

(1)

4f-Transition Metal (Rare Earth) Chalcogenides

253

(2)

Synthesis and Crystal Growth Under Controlled Thermodynamic Parameters

255

(5)

Control of Nonstoichiometry

256

(3)

Chemical Vapor Transport of the Chalcogenides

259

(1)

By Reactions in Chalcogen-Hydrogen Systems

260

(2)

Of Metals

261

(1)

Of Compounds of Metal

261

(1)

By Precipitation Under Normal and Supercritical Conditions

262

(2)

From Aqueous Solution

262

(1)

From Non aqueous Solution

263

(1)

By Insertion Reactions from Solution

264

(31)

Layered Transition Metal Dichalcogenides

269

(1)

Unsolvated Metal Intercalation Compounds: Alkali Metals

269

(5)

Unsolvated Metal Intercalation Compounds: Posttransition Metals

274

(2)

Unsolvated Metal Intercalation Compounds: Transition Metals

276

(1)

``Misfit Layer Compounds''

277

(1)

Solvated Phases

278

(4)

Molecular Intercalation Compounds

282

(2)

Complex Intercalated Species

284

(2)

Other Layered Chalcogenides

286

(1)

Ta2S2C, Nb2S2C

286

(1)

K2Pt4S6 and A2M3S4

287

(1)

MPX3

287

(1)

Li2FeS2, LiCuFeS2, NaCuFeS2 and KCuFeS2

288

(1)

KCu4S3

289

(1)

Chain Structures

290

(1)

The Pseudo---One-Dimensional Compounds MX3

290

(1)

KFeS2

290

(1)

A2[Mo6X6] and [Mo3X3]∞

291

(1)

Framework Structures

292

(1)

Structures with One-Dimensional Channels

292

(1)

Structures with a Three-Dimensional Net of Channels

293

(2)

By Reactions in Melts

295

(4)

In Molten Metals

296

(1)

In Molten Salts

296

(3)

Abbreviations

299

(8)

Author Index

307

(42)

Compound Index

349

(140)

Subject Index

489

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Inorganic Reactions and Methods, The Formation of Bonds to O, S, Se, Te, Po (Part 2)

Summary

Author Biography

Table of Contents

Supplemental Materials

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Inorganic Reactions and Methods, The Formation of Bonds to O, S, Se, Te, Po (Part 2)

Summary

Author Biography

Table of Contents

Supplemental Materials

Digital License