Onium Ions

by Olah, George A.; Laali, Kenneth K.; Wang, Qi; Prakash, G. K. Surya

Edition: 1st

ISBN13: 9780471148777

ISBN10: 0471148776

Format: Hardcover

Pub. Date: 1998-08-11

Publisher(s): Wiley-Interscience

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Summary

Comprehensive and up-to-date coverage of onium ions-an indispensable reference for academic and industrial chemists In Onium Ions, Nobel Prize-winning chemist George Olah joins forces with coauthors Kenneth Laali, Qi Wang, and G. K. Surya Prakash to offer an in-depth look at the chemistry and reactions of these important electron-deficient compounds. While other texts have covered various individual types of onium ions, this work addresses the structure and chemistry of numerous different classes of onium ions. Contents include: * Discussions of well-established classes of onium ions, such as azonium, oxonium, sulfonium, selenonium, telluronium, and phosphonium ions. * Coverage of more recent types, from siliconium, halonium, and carbonium to carboxonium, carbosulfonium, and carbazonium ions. * Clear explanations of definition, classification, preparation, and chemistry of each major group of onium ions. * An exploration of superelectrophilic activation of onium ions through contact with superacid media. Enriched with numerous illustrations and a full listing of references for each chapter, Onium Ions should be a staple text in the professional chemist's library.

Author Biography

GEORGE A. OLAH, PhD, was awarded the 1994 Nobel Prize in Chemistry for his work on carbocation chemistry. Professor Olah, holder of the Loker Chair in Organic Chemistry, also is Director of the Loker Hydrocarbon Research Institute at the University of Southern California.<br> <br> KENNETH K. LAALI, PhD, is Professor of Chemistry at Kent State University in Ohio. His research interests are in onium ions and carbocation chemistry. QI WANG, PhD, is Research Chemist at the Occidental Chemical Corporation in Buffalo, New York. His research interests are in superacid and Friedel-Crafts chemistry.<br> <br> SURYA PRAKASH, PhD, is Professor of Chemistry at the University of Southern California, and holds the Olah Chair in Hydrocarbon Chemistry at the Loker Hydrocarbon Research Institute. His research interests are in hydrocarbon, carbocation, and synthetic organic chemistry.

Preface

1 Introduction

(5)

1.1 Introduction and General Aspects

(3)

References

(2)

2 Azonium Ions

(90)

2.1 Ammonium Ions

(14)

2.1.1 Alkyl(aryl)ammonium Cations

(5)

2.1.2 Nitrogen NMR Studies of Ammonium Cations

(1)

2.1.3 Haloammonium Cations

(1)

2.1.3.1 Perfluroammonium Cation, NF(+)(4)

(1)

2.1.3.2 N,N-Difluoroammonium, NH(2)F(+)(2) and the Elusive Trifluoroammonium, NHF(+)(3) Cation

(1)

2.1.3.3 N-Monoflouroammonium Cations, NFH(+)(3) and MeNH(2)F(+)

(1)

2.1.3.4 N-Chloro-N-methylammonium Salts

(1)

2.1.3.5 Fluoromethylammonium Cations

(1)

2.1.3.6 Multinuclear NMR Studies of Fluoro-and Fluoromethylammonium Cations

(2)

2.1.4 Nitrosoammonium Cations (N-Protonated Nitrosamines)

(1)

2.1.5 Oxoammonium Cations

(1)

2.1.6 N-Acylammonium Salts

(1)

2.1.7 Ammonium Cations as Precursors to Hypervalent N(V) Compounds

(2)

2.1.8 Mass Spectrometric Studies of Ammonium Ions and Their Gas-Phase Host-Guest Chemistry

(1)

2.2 Nitronium and Nitrosonium Ions

(26)

2.2.1 Nitronium Ion, NO(+)(2)

(6)

2.2.2 Dihalonitronium Ions, X(2)NO(+)

(1)

2.2.2.1 Dichloronitronium Ion, CI(2)NO(+)

(1)

2.2.2.2 Diflouronitronium Ion, F(2)NO(+)

(2)

2.2.2.3 Chlorofluoronitronium Ion, ON(CL)F(+)

(1)

2.2.2.4 Trifluoromethyl(fluoro)nitronium Ion, ONCF(3)(F) and Trifluoromethyl(methyl)nitronium Ion, ONCF(3)(Me)(+)

(1)

2.2.3 Dithianitronium, NS(+)(2) and Bis(dihalothia)nitronium, (SX)(2)N(+)Ions

(1)

2.2.4 Nitracidium Ion and DimethyInitracidium Ion

(2)

2.2.5 Nitronium Ions From Nitroalkanes and Nitroarenes

(1)

2.2.5.1 Hydroxynitronium Ions [Protonated Nitroalkanes(-arenes)]

(4)

2.2.5.2 Methoxynitronium Ions (O-Alkylated Nitro Compounds) and Related Lewis Acid Complexes

(3)

2.2.6 Nitrosonium Ion, No(+)

(4)

2.2.7 The Nitrousacidium Ion (O-Protonated Nitrous Acid)

(2)

2.3 Diazomium Ions

(39)

2.3.1 Arylidazonium Ions, Ar-N(+)(2)

(1)

2.3.1.1 Ambident Character of Aryldiazonium Ions

(1)

2.3.1.2 Dediazoniation Mechanism

(1)

2.3.1.3 Reversibility of Heterolytic Dediazoniation

(1)

2.3.1.4 Aryldiazonium Ions in Superacids

(1)

2.3.1.5 Organometalic Aryldiazonium Ions

(1)

2.3.1.6 Cyclophane Diazonium Ions

(1)

2.3.1.7 Fluoroaryldiazonium Ions

(1)

2.3.1.8 Gas-Phase Aryldiazonium Ions

(1)

2.3.1.9 Complexed Aryldiazonium Ions

(4)

2.3.2 Nonaromatic Diazonium Ions

(2)

2.3.2.1 Parent Diazonium Ion, HN(+)(2) (Protonated Dinitrogen)

(1)

2.3.2.2 Methyl-and Ethyldiazonium Ions

(2)

2.3.2.3 Fluorodiazonium Ion

(1)

2.3.2.4 Fluoroalkyldiazonium Ions

(1)

2.3.2.5 Amino(N-alkylamino) Diazonium Ions

(5)

2.3.2.6 Cyano-and Nitrodiazonium Ions

(1)

2.3.2.7 Methoxydiazonium Ions

(2)

2.3.2.8 Hydroxydiazonium Ions

(1)

2.3.2.9 Alkenyl-and Alkynyldiazonium Ions

(1)

2.3.2.9.1 Preparation and Chemistry

(5)

2.3.2.9.2 Theoretical Studies and X-ray Structures

(1)

2.3.2.9.3 O-Alkylation of Alpha-Diazoketones

(1)

2.3.2.9.4 Protonated Alpha-Diazocarbonyl Compounds

(3)

2.3.2.9.5 Solvoltic Generation and Chemistry of Alkynydiazonium Ions

(1)

2.3.2.10 Alicyclic diazonium Ions and Their Chemistry

(2)

2.3.2.11 Heterocyclic Nonaromatic Diazonium Ions

(1)

References

(11)

3 Oxonium Ions

(71)

3.1 Definition and Classification

(1)

3.2 Preparation of Oxonium Ions

(10)

3.2.1 Hydronium Ions, the Parent Oxonium Ions

(1)

3.2.2 Primary Oxonium Ions

(3)

3.2.3 Secondary Oxonium Ions

101

(1)

3.2.4 Tertiary Oxonium Ions and Their Salts

102

(5)

3.3 The Chemistry of Oxonium Ions

107

(44)

3.3.1 The Chemistry of Acidic Oxonium Ions

107

(2)

3.3.2 The Chemistry of Tertiary Oxonium Ions

109

(1)

3.3.2.1 C-Alkylation

109

(1)

3.3.2.2 N-Alkylation

110

(1)

3.3.2.2.1 Alkylation of Amines and Related Compounds

110

(1)

3.3.2.2.2 Alkylation of Imines and Related Compounds

111

(4)

3.3.2.2.3 Alkylation of Nitriles and Related Compounds

115

(2)

3.3.2.2.4 Alkylation of Five-Membered Heterocyclic Aromatic Compounds

117

(1)

3.3.2.2.5 Alkylation of Six-Membered Heterocyclic Aromatic Compounds

118

(2)

3.3.2.3 O-Alkylation

120

(1)

3.3.2.3.1 Alkylation of Alcohols, Ethers, and Related Compounds

120

(2)

3.3.2.3.2 Alkylation of Ketones and Related Compounds

122

(4)

3.3.2.3.3 Esterification of Carboxylic Acids and Alkylation of Esters

126

(1)

3.3.2.3.4 Alkylation of Sulfoxides and Phosphine Oxides

127

(7)

3.3.2.3.5 Alkylation of Sulfoxides and Phosphine Oxides

134

(2)

3.3.2.3.6 Alkylation of Nitrogen-Oxygen-Bond-Containing Compounds

136

(1)

3.3.2.3.7 O-Alkylation of Enolates, Ylides, and Other Anion Bearing Compounds

137

(1)

3.3.2.3.8 Preparation of Fischer Carbene Complexes

138

(1)

3.3.2.3.9 O-Alkylation of Other Metal Complexes

139

(1)

3.3.2.4 S-Alkylation of Sulfides and Related Compounds

140

(1)

3.3.2.4.1 Alkylation of Sulfides and Relateds Compounds

140

(4)

3.3.2.4.2 Alkylation of Thicarbonyl Compounds

144

(1)

3.3.2.4.3 S-Alkylation of Ligands of Transition Metal Complexes

145

(1)

3.3.2.5 Deprotonation of Trialkyloxonium Ions to Oxonium Ylides

146

(2)

3.3.2.6 Miscellaneous Reactions

148

(2)

3.3.3 Reactions of Arylalkyloxonium and Triaryloxonium Ions

150

(1)

References

151

(16)

4 Sulfonium, Selenonium, and Telluronium Ions

167

(36)

4.1 Sulfonium Ions

167

(23)

4.1.1 Trialkyl(aryl)Sulfonium Ions

167

(3)

4.1.2 Acidic Sulfonium Ions

170

(1)

4.1.2.1 Trihydridosulfonium Ion, the Parent Sulfonium Ion

170

(1)

4.1.2.2 Monoalkylsulfonium Ions (Protonated Aliphatic Thiols)

171

(1)

4.1.2.3 Dialkylsulfonium Ions

172

(2)

4.1.2.4 Fluorinated Acidic Sulfonium Ions

174

(1)

4.1.2.5 Acidic Cyclic Sulfonium Ions

175

(1)

4.1.3 Tertiary Halosulfonium Ions

176

(1)

4.1.3.1 Parent SF3+SCI3+SBr3+

176

(1)

4.1.3.2 Dihalo-monoalkyl(perfluoroalkyl)sulfonium Ions

177

(3)

4.1.3.3 Dihalo(pentafluorophenyl)sulfonium Ions

180

(1)

4.1.3.4 Dialkyl(arylalkyl)bromo-and Dialkylchlorosulfonium Ions

181

(2)

4.1.3.5 Diaryl(fluoro)-, Dimethyl(fluoro)-, and Diperfluoroalkyl(fluoro)sulfonium Ions

183

(1)

4.1.4 S-Trifluoromethylated Dibenzothiophenium Ion

183

(1)

4.1.5 Fluorothiosulfonium Ions

184

(1)

4.1.6 Methoxyfluoro(trifluoromethyl)sulfonium Ions

184

(2)

4.1.7 Aminofluorosulfonium Ions

186

(1)

4.1.8 Nitro-and Nitritosulfonium Ions

187

(1)

4.1.9 Cyanosulfonium Ions

188

(1)

4.1.10 Dimercapto(methyl)sulflonium-and Bis(chlorothio)methylsulfonium Ion Salts

189

(1)

4.1.11 Aurated Sulfonium Ions

189

(1)

4.2 Selenonium and Telluronium Ions

190

(9)

4.2.1 Trailkyl(aryl)selenonium and Telluronium Ions

190

(1)

4.2.2 Divinyl-and Dialkylpropynyltelluronium Ions Salts

191

(1)

4.2.3 Cyclical Selenonium Ions

191

(1)

4.2.4 Fluorinate Selenonium and Telluronium Ions

192

(1)

4.2.5 Acidic Selenonium and Telluronium Ions

193

(1)

4.2.5.1 Hydridoselenonium and Telluronium Ions

193

(1)

4.2.5.2 Methylselenonium Ion

193

(1)

4.2.5.3 Dialkylselenonium and Telluronium Ions

194

(1)

4.2.6 Multinuclear NMR studies

194

(1)

4.2.7 Solid-State NMR and X-ray Study of Telluronium Ions

195

(1)

4.2.8 Protosolvation and Alkylation Ability

195

(1)

4.2.9 Haloselenonium and Telluronium Ions

196

(1)

4.2.10 Diselenide Dications

197

(1)

4.2.11 Aurated Selenonium Ions

198

(1)

References

199

(4)

5 Phosphonium and Arsonium Ions

203

(43)

5.1 Phosphonium Ions

203

(29)

5.1.1 Tetraakyl(aryl)phosphonium Ions

204

(3)

5.1.2 Cyclic Phosphonium Ions

207

(4)

5.1.3 NMR and X-ray Spectroscopic Studies of Alkyl(aryl)phosphonium Ions

211

(1)

5.1.4 Aurated Phosphonium Ions

212

(1)

5.1.5 Tetraaryl[(alkyl)(dialkylamino)]phosphonium Dications and Diphosphonyl Ethers

212

(1)

5.1.6 Trimethylsilylphosphonium Ions

213

(1)

5.1.7 Enamine Phosphonium Salts

214

(1)

5.1.8 Halophosphonium and Hydroxyhalophosphonium Ions

215

(4)

5.1.9 Hydroxy(alkoxy)phosphonium Ions

222

(2)

5.1.10 Mercapto-and Methylthiophosphonium Ions and Their Halo Derivatives

224

(3)

5.1.11 Bromosulfinyl(trihalo)phosophonium Ions

227

(1)

5.1.12 Monoprotonated Phosphines and Halophosphines

228

(4)

5.2 Arsonium Ions

232

(10)

5.2.1 Tetraalkyl(vinyl)and Tetraaryl(alkyl)arsonium Ions

233

(2)

5.2.2 (77)As NMR Studies of Arsonium Ions

235

(1)

5.2.3 X-ray Structural Studies of Arsonium Ions

236

(2)

5.2.4 Haloarsonium Ions

238

(1)

5.2.4.1 Fluoroarsonium Ions

238

(1)

5.2.4.2 Chloro-and Iodoarsonium Ions

239

(1)

5.2.5 Hydroxy(alkoxy)arsonium Ions

240

(1)

5.2.6 Acidic Arsonium Ions

240

(1)

5.2.6.1 Hydrido(fluorohydrido)arsonium Ions

240

(1)

5.2.6.2 Protonated Trivinylarsonium Ions

241

(1)

References

242

(4)

6 Halonium Ions

246

(23)

6.1 Introduction

246

(2)

6.2 Acyclic (Open-Chain) Halonium Ions

248

(8)

6.2.1 Alkyl-and Arylhydridohalonium Ions

248

(1)

6.2.2 Dilakyl, Alkyl(vinyl), Divinyl, and Dilakynylalonium Ions

248

(4)

6.2.3 Alkyl(aryl), Alkenyl(aryl), and Alkynyl(aryl)halonium Ions

252

(3)

6.2.4 Diarylhalonium Ions

255

(1)

6.3 Cyclic Halonium Ions

256

(9)

6.3.1 Ethylenehalonium Ions

256

(3)

6.3.2 Trimethylenehalonium Ions

259

(1)

6.3.3 Tetramethylenehalonium Ions

260

(1)

6.3.4 Pentamethylenehalonium Ions

261

(1)

6.3.5 Bicyclic Halonium Ions

262

(2)

6.3.6 Halophenium Ions

264

(1)

References

265

(4)

7 Carboxonium, Carbosulfonium, and Carbazonium Ions

269

(77)

7.1 Carboxonium Ions

270

(34)

7.1.1 Acidic Carboxonium Ions: Preparation and Chemistry

271

(15)

7.1.2 Alkylcarboxonium (Alkoxycarbenium) Ions

286

(1)

7.1.2.1 Preparation

286

(8)

7.1.2.2 Structure and Physical Properties

294

(4)

7.1.2.3 Chemistry of Alkylcarboxonium Ions

298

(7)

7.2 Carbosulfonium Ions

305

(12)

7.2.1 Acidic Carbosulfonium Ions

306

(1)

7.2.2 Tertiary Carbosulfonium Ions

307

(1)

7.2.2.1 Preparation

307

(3)

7.2.2.2 Structure and Physical Properties

310

(2)

7.2.2.3 Chemistry of Carbosulfonium Ions

312

(5)

7.3 Carbazonium Ions

317

(16)

7.3.1 Iminium Ions

317

(1)

7.3.1.1 Preparation and Structure

317

(4)

7.3.1.2 Chemistry of Iminum Ions

321

(5)

7.3.2 Nitrilium Ions

326

(1)

7.3.2.1 Preparation and Structure of Nitrilium Ions

326

(2)

7.3.2.2 Chemistry of Nitrilium Ions

328

(5)

References

333

(13)

8 Carbonium Ions

346

(45)

8.1 General Concept of Carbocation: Carbenium versus Carbonium Ions

346

(3)

8.2 Long-Lived Hypercoordinate (Nonclassic) Carbonium Ions

349

(33)

8.2.1 Alkonium Ions

349

(1)

8.2.1.1 Methonium Ion (CH(+)(5) and Related Ions

350

(4)

8.2.1.2 Ethonium Ion (C(2)H(+)(7) and Related Ions

354

(1)

8.2.1.3 Higher Alkonium Ions

355

(2)

8.2.1.4 Mu-Hydrogen-Bridged Cycloaklonium Ions

357

(2)

8.2.2 Cyclopropylmethyl and Cyclobutyl Cations

359

(3)

8.2.3 2-Norbornyl Cation

362

(7)

8.2.4 2-Bicyclo[2.1.1]hexyl Cation

369

(2)

8.2.5 1,3,5,7-Tetramethyl-2-adamantyl Cation

371

(1)

8.2.6 Bishomocyclopropenium Cations

372

(3)

8.2.7 Trishomocyclopropenium Cations

375

(2)

8.2.8 1,3-Dehydro-5,7-adamantanediyl Dications

377

(1)

8.2.9 Hypercoordinate (Nonclassic) Pyramidal Carbocations

377

(1)

8.2.9.1 (CH(+)(5)-Type Cations

377

(3)

8.2.9.2 (CH(2+)(6)-Type Dications

380

(2)

References and Notes

382

(9)

9 Siliconium Ions

391

(34)

9.1 Differentiation of Trivalent Silicenium from Five-Coordinate Siliconium Ions

391

(1)

9.2 The Significance of Silicocations

392

(1)

9.3 Differentiation of Silicocations from Carbocations

393

(1)

9.4 Gaseous Siliconium Ions

393

(3)

9.4.1 Protonated Silane, the Parent Siliconium Ion, SiH(+)(5)

393

(2)

9.4.2 Silane Radical Cation SiH(++)(4)

395

(1)

9.4.3 Ionization of Organosilanes in the Gas Phase

396

(1)

9.5 Siliconium Ions in Solution

396

(15)

9.5.1 Si(V)(+) Intermediates in Solvolysis

396

(1)

9.5.1.1 S(N)I-Si and S(N)i-Si Systems

396

(2)

9.5.1.2 S(E)i-Si and (S(N)i-S(E)i)Si Systems

398

(1)

9.5.1.3 Siliconium Ion Formation by 1,3-Methyl Migration

399

(1)

9.5.2 Reaction of Trialkyl(aryalkyl)silanes with Diborane

399

(1)

9.5.3 Siliconium Ions in H-D Exchange of R(3)SiH with DI/AII(3)

400

(1)

9.5.4 Siliconium Ion Intermediates in R(3)SiF/SbF(5) Exchanging System

400

(3)

9.5.5 R(3)SiX/Friedel-Crafts Lewis Acid Complexes Involving Siliconium Ion Intermediates

403

(4)

9.5.6 Siliconium Ion Intermediates in Si-C(Si-O) Cleavage Reactions

407

(1)

9.5.6.1 With Protic Superacids and Superelectrophiles

407

(3)

9.5.6.2 Acid Si--C Cleavage Involving Crowded Trisilylmethyl Group

410

(1)

9.6 Beta-Silylcarbenium Ions with Bridging Siliconium Ion Nature

411

(2)

9.7 Siliconium Ions with Bound Donor Ligands

413

(7)

References

420

(5)

10 Onium Dications

425

(62)

10.1 Differentiations of Distonic from Gitonic Onium Dications

425

(3)

10.1.1 Representative Distonic Onium Dications

425

(1)

10.1.1.1 Ammonium Dications

425

(1)

10.1.1.2 Oxonium and Sulfonium Dications

426

(1)

10.1.1.3 Diacyl Cations and Dicarboxonium Ions

426

(1)

10.1.1.4 Onium-Carboxonium Dications

427

(1)

10.1.1.5 Oxonium-Diazonium Dications

427

(1)

10.1.1.6 Onium Polycations

427

(1)

10.2 Gitonic Onium Dications

428

(51)

10.2.1 General Aspects

428

(2)

10.2.2 Oxonium Dications

430

(1)

10.2.2.1 Alkyloxonium Dications

430

(5)

10.2.2.2 Protohydronium Dication (Diprotonated Water)

435

(3)

10.2.3 Carboxonium Dications [Diprotonated (Alkylated) Carbonyl Compounds]

438

(4)

10.2.4 Protonated (Lewis Acid-Complexed) Acyl Dications

442

(3)

10.2.5 Diprotonated Carboxylic Acids

445

(1)

10.2.6 Diprotonated Esters

446

(1)

10.2.7 Diprotonated Carbon Monoxide (Protoformyl Dication)

447

(3)

10.2.8 Protonated and Diprotonated Carbonic Acid and Carbon Dioxide

450

(2)

10.2.9 Sulfonium (Selenonium, Telluronium) Dications

452

(4)

10.2.10 Diprotonated (Alkylated) Thiocarbonyl Compounds, Thiocarboxylic Acids. Thiocarbonic Acid, and Carbonyl Sulfide

456

(1)

10.2.11 Halonium Dications

457

(1)

10.2.11.1 Protonated (Alkylated) Dialkylhalonium Dications

457

(1)

10.2.11.2 Protiohalonium Dications

458

(1)

10.2.12 Diprotonated Alkanes, (Protioalkonium Dications)

459

(1)

10.2.12.1 Diprotonated Methane, (CH)(2+)(6) (Protiomethonium Dication)

459

(3)

10.2.12.2 Diprotonated Ethane. C(2)H(2+)(8) (Protioethonium Dication)

462

(1)

10.2.13 Triprotonated Methane, CH(3+)(7) (Diprotomethonium Trication)

462

(2)

10.2.14 Protioalkyl Dications (Alkane Dications, Carbonium-Carbenium Dications)

464

(1)

10.2.14.1 Protiomethyl Dications (Methane Dication)

464

(1)

10.2.14.2 Protioethyl Dication (Ethane Dication)

465

(1)

10.2.14.3 Protio-tert-butyl Dication (Isobutane Dication, C(4)H (2+)(10)

466

(2)

10.2.14.4 Protio-2-propyl Dication (Propane Dication, C(3)H(2+)(8)

468

(2)

10.2.15 Protio (Lewis Acid-Complexed) Halocarbenium Dications and Their Analogs

470

(4)

10.2.16 Azacarbodications

474

(3)

10.2.17 Diprotonated Nitric Acid and Protonitronium Dication

477

(2)

10.2.18 Aurated Gitonic Onium Dications

479

(1)

10.3 Conclusions and Significance

479

(1)

References and Notes

480

(7)

Index

487

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