Preface to the Second Edition .................................. xv
A Note from the Editors ....................................... xix
Acknowledgements .............................................. xix
List of Contributors .......................................... xxi
Volume 1
1. Introduction ................................................. 1
John S.Wilkes, Peter Wasserscheid, and Tom Welton
2. Synthesis and Purification ................................... 7
2.1. Synthesis of Ionic Liquids ................................. 7
Charles M.Gordon and Mark J.Muldoon
2.1.1. Introduction ........................................ 7
2.1.2. Quaternization Reactions ............................ 9
2.1.3. Anion-exchange Reactions ........................... 13
2.1.3.1. Lewis Acid-based Ionic Liquids ............ 13
2.1.3.2. Anion Metathesis .......................... 14
2.1.4. Purification of Ionic Liquids ...................... 18
2.1.5. Improving the Sustainability of Ionic Liquids ...... 20
2.1.6. Conclusions ........................................ 23
2.2. Quality Aspects and Other Questions Related to
Commercial Ionic Liquid Production ........................ 26
Markus Wagner and Claus Hilgers
2.2.1. Introduction ....................................... 26
2.2.2. Quality Aspects of Commercial Ionic Liquid
Production ......................................... 27
2.2.2.1. Color ..................................... 28
2.2.2.2. Organic Starting Material and Other
Volatiles ................................. 29
2.2.2.3. Halide Impurities ......................... 30
2.2.2.4. Protic Impurities ......................... 32
2.2.2.5. Other Ionic Impurities from Incomplete
Metathesis Reactions ...................... 33
2.2.2.6. Water ..................................... 33
2.2.3. Upgrading the Quality of Commercial Ionic
Liquids ............................................ 34
2.2.4. Novel, Halide-Free Ionic Liquids ................... 34
2.2.5. Scale-up of Ionic Liquid Synthesis ................. 36
2.2.6. Health, Safety and Environment ..................... 37
2.2.7. Corrosion Behavior of Ionic Liquids ................ 41
2.2.8. Recycling of Ionic Liquids ......................... 42
2.3. Synthesis of Task-specific Ionic Liquids .................. 45
James H.Davis, Jr., updated by Peter Wasserscheid
2.3.1. Introduction ....................................... 45
2.3.2. General Synthetic Strategies ....................... 47
2.3.3. Functionalized Cations ............................. 48
2.3.4. Functionalized Anions .............................. 53
2.3.5. Conclusion ......................................... 53
3. Physicochemical Properties .................................. 57
3.1. Physicochemical Properties of Ionic Liquids: Melting
Points and Phase Diagrams ................................. 57
John D.Holbrey and Robin D.Rogers
3.1.1. Introduction ....................................... 57
3.1.2. Measurement of Liquid Range ........................ 59
3.1.2.1. Melting Points ............................ 60
3.1.2.2. Upper Limit - Decomposition Temperature ... 60
3.1.3. Effect of Ion Sizes on Salt Melting Points ......... 62
3.1.3.1. Anion Size ................................ 63
3.1.3.2. Mixtures of Anions ........................ 64
3.1.3.3. Cation Size ............................... 65
3.1.3.4. Cation Symmetry ........................... 66
3.1.3.5. Imidazolium Salts ......................... 67
3.1.3.6. Imidazolium Substituent Alkyl Chain
Length .................................... 68
3.1.3.7. Branching ................................. 69
3.1.4. Summary ............................................ 70
3.2. Viscosity and Density of Ionic Liquids .................... 72
Rob A.Mantz and Paul C.Trulove
3.2.1. Viscosity of Ionic Liquids ......................... 72
3.2.1.1. Viscosity Measurement Methods ............. 73
3.2.1.2. Ionic Liquid Viscosities .................. 75
3.2.2. Density of Ionic Liquids ........................... 86
3.2.2.1. Density Measurement ....................... 86
3.2.2.2. Ionic Liquid Densities .................... 86
3.3. Solubility and Solvation in Ionic Liquids ................. 89
Violina A.Cocalia, Ann E.Visser, Robin D.Rogers,
and John D.Holbrey
3.3.1. Introduction ....................................... 89
3.3.2. Metal Salt Solubility .............................. 90
3.3.2.1. Halometallate Salts ....................... 90
3.3.2.2. Metal Complexes ........................... 91
3.3.3. Extraction and Separations ......................... 92
3.3.4. Organic Compounds .................................. 96
3.3.5. Conclusions ....................................... 101
3.4. Gas Solubilities in Ionic Liquids ........................ 103
Jessica L.Anderson, Jennifer L.Anthony,
Joan F.Brennecke, and Edward J.Maginn
3.4.1. Introduction ...................................... 103
3.4.2. Experimental Techniques 104
3.4.2.1. Gas Solubilities and Related
Thermodynamic Properties ................. 104
3.4.2.2. The Stoichiometric Technique ............. 106
3.4.2.3. The Gravimetric Technique ................ 107
3.4.2.4. Spectroscopic Techniques ................. 107
3.4.2.5. Gas Chromatography ....................... 108
3.4.3. Gas Solubilities .................................. 108
3.4.3.1. CO2 ...................................... 109
3.4.3.2. Reaction Gases (O2, H2, CO) .............. 117
3.4.3.3. Other Gases (N2, Ar, CH4, C2H6, C2H4,
H20, S02, CHF3, etc.) .................... 121
3.4.3.4. Mixed Gases .............................. 122
3.4.3.5. Enthalpies and Entropies ................. 123
3.4.4. Applications ...................................... 123
3.4.4.1. Reactions Involving Gases ................ 124
3.4.4.2. Gas Storage .............................. 125
3.4.4.3. Gas Separations .......................... 125
3.4.4.4. Extraction of Solutes from Ionic
Liquids with Compressed Gases or
Supercritical Fluids ..................... 126
3.4.5. Summary ........................................... 126
3.5. Polarity ................................................. 130
Tom Welton
3.5.1. Microwave Dielectric Spectroscopy ................. 131
3.5.2. Chromatographic Measurements ...................... 131
3.5.3. Absorption Spectra ................................ 133
3.5.4. Antagonistic Behavior in Hydrogen Bonding ......... 136
3.5.5. Fluorescence Spectra .............................. 137
3.5.6. Refractive Index .................................. 137
3.5.7. EPR Spectroscopy .................................. 138
3.5.8. Chemical Reactions ................................ 138
3.5.9. Comparison of Polarity Scales ..................... 138
3.5.10.Conclusions ....................................... 140
3.6. Electrochemical Properties of Ionic Liquids .............. 141
Robert A. Mantz
3.6.1. Electrochemical Potential Windows ................. 242
3.6.2. Ionic Conductivity ................................ 150
3.6.3. Transport Properties .............................. 165
4. Molecular Structure and Dynamics ........................... 175
4.1. Order in the Liquid State and Structure .................. 175
Chris Hardacre
4.1.1. Neutron Diffraction ............................... 175
4.1.2. Formation of Deuterated Samples ................... 176
4.1.3. Neutron Sources ................................... 177
4.1.3.1. Pulsed (Spallation) Neutron Sources ...... 177
4.1.3.2. Reactor Sources .......................... 178
4.1.4. Neutron Cells for Liquid Samples .................. 178
4.1.5. Examples .......................................... 178
4.1.5.1. Binary Mixtures .......................... 179
4.1.5.2. Simple Salts ............................. 182
4.1.6. X-ray Diffraction ................................. 184
4.1.6.1. Cells for Liquid Samples ................. 184
4.1.6.2. Examples ................................. 185
4.1.7. Extended X-ray Absorption Fine Structure
Spectroscopy ...................................... 190
4.1.7.1. Experimental ............................. 191
4.1.7.2. Examples ................................. 193
4.1.8. X-ray and Neutron Reflectivity .................... 199
4.1.8.1. Experimental Set-up ...................... 199
4.1.8.2. Examples ................................. 200
4.1.9. Direct Recoil Spectrometry (DRS) .................. 201
4.1.9.1. Experimental Set-up ...................... 202
4.1.9.2. Examples ................................. 202
4.1.10.Conclusions ....................................... 203
4.2. Computational Modeling of Ionic Liquids .................. 206
Patricia A.Hunt, Edward J.Maginn, Ruth
M.Lynden-Bell, and Mario G.Del Popolo
4.2.1. Introduction ...................................... 206
4.2.1.1. Classical MD ............................. 209
4.2.1.2. Ab initio Quantum Chemical Methods ....... 210
4.2.1.3. Ab initio MD ............................. 211
4.2.1.4. Using Ab Initio Quantum Chemical
Methods to Study Ionic Liquids ........... 211
4.2.2.1. Introduction ............................. 211
4.2.2.2. Acidic Haloaluminate and Related Melts ... 212
4.2.2.3. Alkyl Imidazolium-based Ionic Liquids .... 214
4.2.2.4. The Electronic Structure of Ionic
Liquids .................................. 218
4.2.3. Atomistic Simulations of Liquids .................. 220
4.2.3.1. Atomistic Potential Models for Ionic
Liquid Simulations ....................... 221
4.2.3.1. Atomistic Simulations of Neat Ionic
Liquids - Structure and Dynamics ......... 226
4.2.4. Simulations of Solutions and Mixtures ............. 236
4.2.5. Simulations of Surfaces ........................... 239
4.2.6. Ab initio Simulations of Ionic Liquids ............ 239
4.2.7. Chemical Reactions and Chemical Reactivity ........ 244
4.3. Translational Diffusion .................................. 249
Joachim Richter, Axel Leuchter, and Gunter Palmer
4.3.1. Main Aspects and Terms of Translational
Diffusion ......................................... 249
4.3.2. Use of Translational Diffusion Coefficients ....... 251
4.3.3. Experimental Methods .............................. 252
4.3.4. Results for Ionic Liquids ......................... 254
4.4. Molecular Reorientational Dynamics ....................... 255
Andreas Dolle, Phillip G.Wahlbeck, and W.Robert
Carper
4.4.1. Introduction ...................................... 255
4.4.2. Experimental Methods .............................. 256
4.4.3. Theoretical Background ............................ 257
4.4.4. Results for Ionic Liquids ......................... 258
4.4.5. Chemical Shift Anisotropy Analysis ................ 261
4.4.6. Stepwise Solution of the Combined Dipolar and
NOE Equations ..................................... 261
4.4.7. NMR-Viscosity Relationships ....................... 264
5. Organic Synthesis .......................................... 265
5.1. Ionic Liquids in Organic Synthesis: Effects on Rate
and Selectivity .......................................... 265
Cinzia Chiappe
5.1.1. Introduction ...................................... 265
5.1.2. Ionic Liquid Effects on Reactions Proceeding
through Isopolar and Radical Transition States .... 268
5.1.2.1. Energy Transfer, Hydrogen Transfer
and Electron Transfer Reactions .......... 268
5.1.2.2. Diels-Alder Reactions .................... 272
5.1.2.3. Ionic Liquid Effects on Reactions
Proceeding through Dipolar Transition
States ................................... 274
5.1.3.1. Nucleophilic Substitution Reactions ...... 275
5.1.3.2. Electrophilic Addition Reactions ......... 284
5.1.3.3. Electrophilic Substitution Reactions ..... 287
5.1.4. Conclusions ....................................... 289
5.2. Stoichiometric Organic Reactions and Acid-catalyzed
Reactions in Ionic Liquids ............................... 292
Martyn Parle
5.2.1. Electrophilic Reactions ........................... 294
5.2.1.1. Friedel-Crafts Reactions ................. 294
5.2.1.2. Scholl and Related Reactions ............. 310
5.2.1.3. Cracking and Isomerization Reactions ..... 312
5.2.1.4. Electrophilic Nitration Reactions ........ 315
5.2.1.5. Electrophilic Halogenation Reactions ..... 316
5.2.1.6. Electrophilic Phosphylation Reactions .... 318
5.2.1.7. Electrophilic Sulfonation Reactions ...... 318
5.2.2. Nucleophilic Reactions ............................ 319
5.2.2.1. Aliphatic Nucleophilic Substitution
Reactions ................................ 319
5.2.2.2. Aromatic Nucleophilic Substitution
Reactions ................................ 326
5.2.3. Electrocyclic Reactions ........................... 327
5.2.3.1. Diels-Alder Reactions .................... 327
5.2.3.2. Hetero Diels-Alder Reactions ............. 330
5.2.3.3. The Ene Reaction ......................... 332
5.2.4. Addition Reactions (to C=C and C=0 Double
Bonds) ............................................ 334
5.2.4.1. Esterification Reactions (Addition
to C=0) .................................. 334
5.2.4.2. Amide Formation Reactions (Addition
to C=0) .................................. 335
5.2.4.3. The Michael Reaction (Addition to C=C) ... 336
5.2.4.4. Methylene Insertion Reactions
(Addition to C=0 and C=C) ................ 339
5.2.4.5. Addition Reactions Involving
Organometallic Reagents .................. 340
5.2.4.6. Miscellaneous Addition Reactions ......... 344
5.2.5. Condensation Reactions ............................ 345
5.2.5.1. General Condensation Reactions ........... 345
5.2.5.2. The Mannich Reaction ..................... 349
5.2.6. Oxidation Reactions ............................... 350
5.2.6.1. Functional Group Oxidation Reactions ..... 350
5.6.6.1. Epoxidation and Related Reactions ........ 353
5.2.6.1. Miscellaneous Oxidation Reactions ........ 355
5.2.7. Reduction Reactions ............................... 356
5.2.8. Miscellaneous Reactions in Ionic Liquids .......... 358
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