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Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes : Catalysis by Metal Complexes - Alexander Evgen'evich Shilov

Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes

Catalysis by Metal Complexes

Hardcover

Published: 31st March 2000
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hemistry is the science about breaking and forming of bonds between atoms. One of the most important processes for organic chemistry is breaking bonds C-H, as well as C-C in various compounds, and primarily, in hydrocarbons. Among hydrocarbons, saturated hydrocarbons, alkanes (methane, ethane, propane, hexane etc. ), are especially attractive as substrates for chemical transformations. This is because, on the one hand, alkanes are the main constituents of oil and natural gas, and consequently are the principal feedstocks for chemical industry. On the other hand, these substances are known to be the less reactive organic compounds. Saturated hydrocarbons may be called the "noble gases of organic chemistry" and, if so, the first representative of their family - methane - may be compared with extremely inert helium. As in all comparisons, this parallel between noble gases and alkanes is not fully accurate. Indeed the transformations of alkanes, including methane, have been known for a long time. These reactions involve the interaction with molecular oxygen from air (burning - the main source of energy!), as well as some mutual interconversions of saturated and unsaturated hydrocarbons. However, all these transformations occur at elevated temperatures (higher than 300-500 °C) and are usually characterized by a lack of selectivity. The conversion of alkanes into carbon dioxide and water during burning is an extremely valuable process - but not from a chemist viewpoint.

Prefacep. xi
Introductionp. 1
Referencesp. 4
Processes of C-H Bond Activationp. 8
Chemical Reactivity of Hydrocarbonsp. 8
Cleavage of the C-H Bond Promoted by Metal Complexesp. 11
Three Types of Processesp. 11
Mechanisms of the C-H Bond Cleavagep. 16
Brief History of Metal-Complex Activation of C-H Bondsp. 17
Referencesp. 19
Hydrocarbon Transformations That Do Not Involve Metals or Their Compoundsp. 21
Transformations Under the Action of Heat or Irradiationp. 21
Pyrolysisp. 21
Photolysisp. 24
Radiolysisp. 24
Reactions with Atoms, Free Radicals and Carbenesp. 25
Halogenationp. 30
Reactions with Oxygen- and Nitrogen-containing Radicalsp. 33
Reactions with Carbenesp. 35
Reactions with Participation of Ion Radicalsp. 36
Oxidation by Molecular Oxygenp. 37
High-temperature Oxidation in the Gas Phasep. 37
Non-catalyzed Autoxidation in the Liquid Phasep. 46
Photochemical Oxidation in the Liquid Phasep. 51
Other Reactions Initiated by Radicalsp. 55
Oxidation with Oxygen-containing Compoundsp. 57
Peroxidesp. 58
Dioxiranesp. 59
Carboxylationp. 62
Electrophilic Substitution of Hydrogen in Alkanesp. 63
Transformations in the Presence of Superacidsp. 63
Reactions with Novel Electrophilic Reagentsp. 65
Referencesp. 69
Heterogeneous Hydrocarbon Reactions with Participation of Solid Metals and Metal Oxidesp. 76
Mechanisms of the Interaction between Alkanes and Catalyst Surfacesp. 78
Isotope Exchangep. 79
Isomerizationp. 83
Dehydrogenation and Dehydrocyclizationp. 86
Hydrogenolysisp. 89
Heterogeneous Oxidationp. 90
Oxygenation with Molecular Oxygenp. 90
Oxygenation with Other Oxidantsp. 96
Oxidative Dehydrogenation and Dehydrocyclizationp. 101
Oxidative Dimerization of Methanep. 104
Oxidative and Nonoxidative Condensation of Alkanesp. 105
Homologationp. 105
Aromatization of Light Alkanesp. 106
Khcheyan's Reactionp. 108
Functionalization of C-H Compoundsp. 109
Referencesp. 111
Activation of C-H Bonds by Low-Valent Metal Complexes ("the Organometallic Chemistry")p. 127
Formation of andsigma;-Organyl Hydride Complexesp. 128
Cyclometalationp. 129
Intermolecular Oxidative Additionp. 130
Formation of Some Other Productsp. 142
Splitting the C-H Bond Activated by Polar Substituentsp. 156
Replacing Hydrogen Atoms by Various Groupsp. 157
Isotope Exchangep. 158
Dehydrogenationp. 162
Introduction of Carbonyl Groups into Hydrocarbon Moleculesp. 168
Other Functionalizationsp. 170
Functionalization of C-H Bonds with Intermediate Formation of Radicals and Carbenesp. 175
Radicals in C-H Bond Functionalizationp. 175
Insertion of Carbenes into C-H Bondsp. 177
Cleavage of Some Other Bondsp. 181
Activation of C-C Bondsp. 181
Activation of Si-H Bondsp. 185
Activation of C-F Bondsp. 186
Activation of Carbon-Element, Element-Element, and Element-Hydrogen Bondsp. 187
Referencesp. 188
Hydrocarbon Activation by Metal Ions, Atoms, and Complexes in the Gas Phase and in a Matrixp. 200
Reactions with Metal Ions, Atoms, and Complexes in the Gas Phasep. 200
Thermal Reactions with Naked Ions and Atomsp. 200
Thermal Reactions with Ligated Metal Ionsp. 209
Reactions with Photoexcited Metal Ionsp. 210
Reactions with Metal Atoms in a Matrixp. 211
Referencesp. 215
Mechanisms of C-H Bond Splitting by Low-Valent Metal Complexesp. 219
Weak Coordination of Metal Ions with H-H and C-H Bondsp. 219
Formation of "Agostic" Bondsp. 220
Unstable Adducts between Alkanes and Metal Complexesp. 224
Mechanistic Studiesp. 235
Thermodynamics of Oxidative Additionp. 239
Quantum-Chemical Calculationsp. 241
Activation by Bare Metal Ions and Atomsp. 242
Oxidative Addition of C-H and C-C Bonds to Metal Complexesp. 245
Other Processesp. 249
Referencesp. 253
Activation of Hydrocarbons by Platinum Complexesp. 259
Non-Oxidative Reactions in the Presence of Pt(II)p. 259
Some Peculiarities of H-D Exchangep. 261
Multiple H-D Exchangep. 267
Oxidation of Alkanes by Pt(IV) in the Presence of Pt(II)p. 275
Main Peculiarities of Alkane Oxidation by the System "Pt(IV)+Pt(II)"p. 275
Kinetics of the Oxidationp. 276
Activation of Some Other C-H Compoundsp. 282
Photochemical Reactions of PtCl[subscript 6 superscript 2-] with Alkanesp. 284
On the Mechanism of Alkane Activationp. 285
Stages of the Process. Formation of Organometallicsp. 285
Interaction between Pt(II) and Alkanesp. 289
[sigma]-Aryl Complexes of Pt(IV) Formed in Thermal and Photochemical Reactions of Aromatic Hydrocarbons with Pt(IV) Halide Complexesp. 302
The Thermal Reaction of Arenes with PtCl[subscript 6 superscript 2-]p. 302
Photoelectrophilic Substitution in Arenesp. 308
Referencesp. 313
Hydrocarbon Reactions with High-Valent Metal Complexesp. 318
Electrophilic Metalation of C-H Bonds ("Organometallic Activation")p. 318
Metalation of Aromatic Compoundsp. 318
Metalation of sp[superscript 3]-C-H Bondsp. 326
Some Special Casesp. 328
Oxidation in Aqueous and Acidic Media Promoted by Metal Cations and Complexesp. 335
Kinetics and Features of the Oxidation in Aqueous and Acidic Mediap. 336
Alkane Functionalizations in Protic Mediap. 339
On the Mechanisms of Alkane Activation in Aqueous and Acidic Mediap. 345
Oxidation of Arylaalkanes by Metal Cationsp. 349
Oxidations by Metal Oxo Complexesp. 350
Oxygenation of Alkanes with Cr(VI) Derivativesp. 351
Oxygenation of Hydrocarbons with Mn(VII) Compoundsp. 354
Oxygenations by Other Complexesp. 356
Alkane Functionalization under the Action of Polyoxometalatesp. 358
Oxygenation by Peroxo Complexesp. 360
Referencesp. 363
Homogeneous Catalytic Oxidation of Hydrocarbons by Molecular Oxygenp. 371
Transition Metal Complexes in the Thermal Autoxidation of Hydrocarbonsp. 371
Classical Radical-Chain Autoxidationp. 371
Some New Autoxidation Processesp. 384
Coupled Oxidation of Hydrocarbonsp. 391
Earlier Worksp. 392
Gif Systemsp. 402
Other Systems Involving O[subscript 2] and a Reducing Reagentp. 404
Photoinduced Metal-Catalyzed Oxidation of Hydrocarbons by Airp. 409
Referencesp. 421
Homogeneous Catalytic Oxidation of Hydrocarbons by Peroxides and Other Oxygen Atom Donorsp. 430
Oxidation by Hydrogen Peroxidep. 431
Alkyl Hydroperoxides as Productsp. 431
Metal-Catalyzed Oxidations with H[subscript 2]O[subscript 2]p. 435
Oxygenations by Alkyl Hydroperoxidesp. 447
Oxygenations by Peroxyacidsp. 451
Oxidations by Other Oxygen Atom Donorsp. 451
Referencesp. 458
Oxidation in Living Cells and Its Chemical Modelsp. 466
Heme-Containing Monooxygenasesp. 471
Cytochrome P450p. 472
Other Monooxygenasesp. 476
Non-Heme Iron-Containing Monooxygenasesp. 477
Methane Monooxygenasep. 477
Other None-Heme Iron-Containing Oxygenasesp. 481
Mechanisms of Monooxygenationsp. 482
Other Oxygenases Containing Ironp. 487
Copper-Containing Enzymesp. 490
Molybdenum-Containing Enzymesp. 491
Manganese-Containing Enzymesp. 493
Vanadium-Containing Enzymesp. 493
Chemical Models of Enzymesp. 494
Models of Cytochrome P450p. 494
Models of Iron-Containing Non-Heme Oxygenasesp. 500
Models of Other Enzymesp. 501
Anaerobic Oxidation of Alkanesp. 503
Referencesp. 505
Conclusionp. 523
Abbreviationsp. 524
Indexp. 525
Table of Contents provided by Syndetics. All Rights Reserved.

ISBN: 9780792361015
ISBN-10: 0792361016
Series: Catalysis by Metal Complexes
Audience: Professional
Format: Hardcover
Language: English
Number Of Pages: 536
Published: 31st March 2000
Publisher: Springer
Country of Publication: NL
Dimensions (cm): 23.5 x 15.5  x 3.18
Weight (kg): 2.17