Palladacycles: Synthesis, Characterization and Applications

Palladacycles......Page 4
Contents......Page 8
List of Contributors......Page 14
1.2 Definition......Page 18
1.3 Historical Overview......Page 19
1.4 Classification of Palladacycles (Types)......Page 20
1.5 Final Remarks......Page 25
References......Page 26
2.1 General Remarks......Page 30
2.2 Activation of Aryl C–H Bonds......Page 32
2.2.1 Donor Group Coordination......Page 34
2.3 Pincer Complexes: A Special Case......Page 36
2.4 Transcyclometallation......Page 38
2.5 Activation of Heterocyclic C–H Bonds, Formation of Pd–Carbene Bonds......Page 41
2.6.1 Activation of Benzylic C–H Bonds......Page 44
2.6.2 Activation of Aliphatic C–H Bonds......Page 46
References......Page 48
3.2 Oxidative Addition......Page 52
3.3 Transmetallation......Page 68
References......Page 81
4.2 Synthesis of Palladacycles via Nucleophile-Palladation Reaction of Olefins or Alkynes Bearing Electron-Donor Heteroatoms......Page 86
4.2.1 Alkoxypalladation Reaction......Page 87
4.2.2 Carbopalladation......Page 90
4.2.3 Chloropalladation......Page 92
4.3.1 Insertion of Olefins or Alkynes Bearing Electron-Donor Atoms......Page 96
4.3.2 Insertion of Olefins, Allenes or Alkynes into a Pd–C σ-Bond of a Fragment Containing Electron-Donor Atoms......Page 98
4.4.1 Aminopalladation and Aminoformylpalladation......Page 100
References......Page 101
5.2 Reactions with Carbon Monoxide......Page 104
5.3 Reactions with Alkenes......Page 109
5.4 Reaction with Alkynes......Page 110
5.5 Reaction with Isocyanides......Page 117
5.6 Reaction with Allenes......Page 119
5.8 Reaction with Halogens......Page 121
5.9 Conclusions......Page 122
References......Page 123
6.2 Stoichiometric C–H Activation Chemistry......Page 126
6.3.1 Vinylations......Page 128
6.4 Arylations......Page 130
6.5 Direct C–H C–H Coupling Reactions......Page 133
6.7.1 Carbonylations......Page 135
6.7.2 C–N Bond Formation......Page 136
References......Page 137
7.1 Introduction......Page 140
7.2 Resolution Methods......Page 141
7.3 Chiral Palladacyclic Auxiliaries......Page 142
7.4.1 Resolution of Phosphines and Arsines......Page 145
7.4.2 Resolution of Air-Sensitive Ligands......Page 149
7.4.3 Resolution of Atropoisomeric Phosphines......Page 151
7.4.4 Resolution of Halogenophosphines......Page 152
7.4.6 Resolution of Cluttered Chiral Bidentate Ligands......Page 154
7.5.1 Neutral Ligands......Page 157
7.5.2 Anionic Ligands......Page 165
References......Page 168
8.1.1 Introduction......Page 172
8.1.2 Mechanism......Page 173
8.1.3 Catalysts......Page 186
8.2.1 Introduction......Page 203
8.2.2 Mechanism......Page 205
8.2.3 Catalysts......Page 208
References......Page 217
9.1 Introduction......Page 226
9.2 Phosphorus-Based Palladacycles and Pincer Complexes......Page 228
9.3 Nitrogen-Based Palladacycles......Page 230
9.4 Sulfur-Based Palladacycles......Page 232
9.5 Phosphine and Carbene Adducts of Palladacycles......Page 233
9.7 Palladacyclic Catalysts for Buchwald–Hartwig Amination......Page 236
9.8 What Are the True Active Catalysts?......Page 237
References......Page 240
10.2 Chiral Palladacycles in Aldol and Related Transformations......Page 244
10.3 Catalytic Allylic Rearrangements......Page 245
10.4 Catalytic C–C Bond-Forming Reactions......Page 246
10.5 Oxidations Involving Palladacycles......Page 249
10.6 Conclusion......Page 252
References......Page 254
11.2 Liquid Crystals......Page 256
11.2.1 Thermotropic Liquid Crystals......Page 257
11.2.2 Nematic Phase......Page 258
11.2.3 Smectic Phases......Page 259
11.2.5 Chiral Mesophases......Page 260
11.4 Liquid Crystalline Ortho-Palladated Complexes......Page 261
11.4.1 Ortho-Palladated Azobenzene Complexes......Page 262
11.4.2 Ortho-Metallated Azoxybenzene Complexes......Page 266
11.4.3 Ortho-Palladated Benzalazine Complexes......Page 267
11.4.4 Ortho-Metallated Imine Complexes......Page 268
11.4.5 Ortho-Metallated Pyrimidine Complexes......Page 286
11.4.6 Ortho-Metallated Pyridazine Complexes......Page 291
11.4.7 Other Ortho-Metallated Complexes......Page 292
References......Page 295
12.1 Introduction......Page 302
12.2 The Early Days......Page 303
12.3 Electronic Absorption Spectra of Cyclopalladated Complexes......Page 304
12.4.1 Azobenzene Palladacycles......Page 310
12.4.2 Palladacycles with Other Orthometallating Bidentate Ligands......Page 313
12.4.3 Luminescent Palladacycles with Terdentate Ligands......Page 314
References......Page 320
13.2.1 Hydrolysis of Activated Esters......Page 324
13.2.2 Enantioselective Hydrolysis of Activated Esters......Page 331
13.2.3 Hydrolysis of Phosphoric Acid Esters......Page 335
13.3 Biologically Relevant Deoxygenation of Dimethyl Sulfoxide by Orthoplatinated Oximes: Oxidoreductase Mimetics......Page 342
13.5 Inhibitors of Enzymatic Activity......Page 344
13.6 Medical Applications......Page 346
References......Page 353
14.1 Introduction......Page 358
14.2 Palladacycles Derived from Aromatic Imines and Thioethers......Page 360
14.3 Pincer Palladacycles: PC(sp(2))P......Page 362
14.4 Pincer Palladacycles: PC(sp(3))P......Page 366
14.5 Pincer Palladacycles: SC(sp(2))S......Page 370
14.6 Related Complexes from Other Groups......Page 371
14.7 Catalysis......Page 372
14.8 Summary and Outlook......Page 373
References......Page 374
15.1.2 Dendrimers in Catalysis......Page 378
15.1.3 Metallodendrimers......Page 379
15.2.1.1 Dendritic Bis-Diphenylphosphino Palladium Complexes......Page 381
15.2.1.2 Other Periphery-Bound Palladium Complexes......Page 383
15.2.1.3 Dendrimers and Star-Shaped Molecules Containing Covalent Pd–C Bonds......Page 384
15.2.2 Dendrimer-Encapsulated Palladium Nanoparticles......Page 386
15.2.3 Miscellaneous......Page 388
15.3.1 The ECE-Pincer Complex: An Introduction......Page 391
15.3.2 Pincer-Palladium Complexes on Star-Shaped Molecules......Page 393
15.3.3 Non-covalently Bound Dendrimer–Pincer Palladium Complexes: Dendritic Catalysts......Page 397
15.3.4 Non-covalently Bound Dendrimer–Pincer Palladium Complexes: Self-Assembled Dendrimers......Page 399
15.3.5 EC-Half-Pincer Palladium Complexes on Dendrimers......Page 406
15.3.6 Dendrimers Containing Functional Groups in the Vicinity of Palladacycles......Page 407
15.3.7 ECE-Pincer Palladium Complexes on Polymers......Page 408
15.4 Concluding Remarks......Page 411
References......Page 412
Index......Page 416