Mechanisms in Homogeneous and Heterogeneous Epoxidation Catalysis
by OyamaFormat: Hardcover
Pub. Date: 2008-09-10
Publisher(s): Elsevier Science
Other versions by this Author
-
Complimentary 7-Day eTextbook Access - Read more
When you rent or buy this book, you will receive complimentary 7-day online access to the eTextbook version from your PC, Mac, tablet, or smartphone. Feature not included on Marketplace Items.
List Price: $246.09
Buy New
Usually Ships in 8 - 10 Business Days.
$234.37
Rent Textbook
Select for Price
Digital
$258.00*
Used Textbook
We're Sorry
Sold Out
How Marketplace Works:
- This item is offered by an independent seller and not shipped from our warehouse
- Item details like edition and cover design may differ from our description; see seller's comments before ordering.
- Sellers much confirm and ship within two business days; otherwise, the order will be cancelled and refunded.
- Marketplace purchases cannot be returned to eCampus.com. Contact the seller directly for inquiries; if no response within two days, contact customer service.
- Additional shipping costs apply to Marketplace purchases. Review shipping costs at checkout.
Summary
The catalytic epoxidation of olefins plays an important role in the industrial production of several commodity compounds, as well as in the synthesis of many intermediates, fine chemicals, and pharmaceuticals. The scale of production ranges from millions of tons per year to a few grams per year. The diversity of catalysts is large and encompasses all the known categories of catalyst type: homogeneous, heterogeneous, and biological. This book summarizes the current status in these fields concentrating on rates, kinetics, and reaction mechanisms, but also covers broad topics including modeling, computational simulation, process concepts, spectroscopy and new catalyst development. The similarities and distinctions between the different reaction systems are compared, and the latest advances are described. * Comprehensive listing of epoxide products * Broad comparison of turnover frequencies of homogeneous, hetergeneous, main-group, biomimetic and biological catalysts * Analysis of the general strengths and weaknesses of varied catalytic systems * Detailed description of the mechanisms of reaction for classical and emerging catalysts
Table of Contents
| Contributors | p. xiii |
| Preface | p. xix |
| Introduction | p. 1 |
| Rates, Kinetics, and Mechanisms of Epoxidation: Homogeneous, Heterogeneous, and Biological Routes | p. 3 |
| Introduction | p. 4 |
| Epoxide Uses and Markets | p. 5 |
| Catalysts and Rates in Commodity and Heterogeneous Epoxidation Processes | p. 12 |
| Catalysts and Rates in Homogeneous Epoxidation Reactions | p. 16 |
| Catalysts and Rates in Biomimetic Epoxidation Reactions | p. 25 |
| Catalysts and Rates in Biological Epoxidation Reactions | p. 28 |
| Summary and Perspective on the Reactivity Results | p. 30 |
| Oxidants for Epoxidation | p. 35 |
| Mechanisms | p. 37 |
| Homogeneous Epoxidation by Early Transition Metals (Lewis Acid Mechanism) | p. 47 |
| Main Group Elements | p. 57 |
| Homogeneous Epoxidation by Late Transition Metals (Redox Mechanism) | p. 59 |
| Biological Systems | p. 70 |
| Perspective and Conclusions | p. 71 |
| Acknowledgments | p. 72 |
| References | p. 72 |
| Homogeneous Catalysis | p. 101 |
| Unprecedented Selectivity in the H[subscript 2]O[subscript 2] Epoxidation of Simple Alkenes Imparted by Soft Pt(II) Lewis Acid Catalysts | p. 103 |
| Introduction | p. 104 |
| Catalyst Synthesis and Lewis Acid Properties | p. 105 |
| General Epoxidation Activity | p. 106 |
| Regioselectivity | p. 107 |
| Diastereoselectivity | p. 108 |
| Enantioselectivity | p. 109 |
| Reactions in Micellar Media | p. 110 |
| Reaction Mechanism | p. 113 |
| Conclusions | p. 113 |
| References | p. 115 |
| Lewis Acid Catalyzed Epoxidation of Olefins Using Hydrogen Peroxide: Prowing Prominence and Expanding Range | p. 119 |
| Introduction | p. 120 |
| Industrial Processes for Propylene Oxide Manufacture: Present and Future | p. 123 |
| A New Pressure Intensified Epoxidation Process for Light Olefins | p. 126 |
| Expanding Range of Lewis Acid Catalysis Chemistry | p. 130 |
| Mid- to Late Transition Metal Catalysts also Perform Epoxidation Reactions by the Lewis Acid Mechanism | p. 131 |
| Acknowledgments | p. 148 |
| References | p. 149 |
| Activation of Hydrogen Peroxide by Polyoxometalates | p. 155 |
| Introduction | p. 156 |
| Activation of Hydrogen Peroxide by Polyoxometalates | p. 157 |
| Catalytic Oxidation by Polyoxometalates | p. 166 |
| Conclusions | p. 170 |
| Future View | p. 170 |
| Acknowledgments | p. 171 |
| References | p. 171 |
| Oxaziridinium Salt-Mediated Catalytic Asymmetric Epoxidation | p. 177 |
| Introduction | p. 178 |
| Page Group Findings | p. 184 |
| Acknowledgments | p. 214 |
| References | p. 214 |
| Selective Aerobic Radical Epoxidation of [alpha]-Olefins Catalyzed by N-Hydroxyphthalimide | p. 217 |
| Introduction | p. 218 |
| Experimental | p. 219 |
| Results and Discussion | p. 220 |
| Conclusions | p. 227 |
| Acknowledgments | p. 227 |
| References | p. 227 |
| Heterogeneous Catalysis | p. 231 |
| Investigation of the Origins of Selectivity in Ethylene Epoxidation on Promoted and Unpromoted Ag/[alpha]-Al[subscript 2]O[subscript 3] Catalysts: A Detailed Kinetic, Mechanistic and Adsorptive Study | p. 233 |
| Introduction | p. 234 |
| The Detailed Kinetics of the Adsorption and Desorption of Oxygen on Silver and the Structure of the Oxide Overlayer and Reaction Conditions | p. 235 |
| The Adsorption of Ethylene and Ethylene Oxide on Clean and Oxidised Ag(111) and Ag(110) | p. 240 |
| The Reaction Mechanism | p. 242 |
| Subsurface Oxygen | p. 247 |
| Promotion | p. 249 |
| The Detailed Kinetics of the Adsorption and Desorption of Ethylene on an Unoxidised and Oxidised Ag/[alpha]-Al[subscript 2]O[subscript 3] Catalyst | p. 254 |
| The Detailed Kinetics of the Adsorption and Desorption of Ethylene on an Oxidised Ag/[alpha]-Al[subscript 2]O[subscript 3] Catalyst Subtending the [alpha subscript 1]-O State Only | p. 255 |
| The Detailed Kinetics of the Adsorption and Desorption of Ethylene on the [alpha subscript 2]-O State Principally | p. 257 |
| Ethylene Desorption from an Unoxidised and Oxidised Cs-Promoted Ag/[alpha]-Al[subscript 2]O[subscript 3] Catalyst | p. 257 |
| The Desorption of Ethylene from an Oxidised Cl-Promoted Cs/Ag/[alpha]-Al[subscript 2]O[subscript 3] Catalyst | p. 258 |
| Overall Conclusions | p. 259 |
| Acknowledgement | p. 261 |
| References | p. 261 |
| Computational Strategies for Identification of Bimetallic Ethylene Epoxidation Catalysts | p. 265 |
| Introduction | p. 266 |
| Computational Details | p. 267 |
| Activation Energies on Ag | p. 270 |
| Extension to Ag-Based Bimetallic Catalysts | p. 272 |
| Predictions Using Microkinetic Modeling | p. 276 |
| Conclusions | p. 279 |
| Acknowledgments | p. 279 |
| References | p. 279 |
| Effect of Support on Ethylene Epoxidation on Ag, Au, and Au-Ag Catalysts | p. 283 |
| Introduction | p. 284 |
| Experimental | p. 285 |
| Results and Discussion | p. 287 |
| Conclusions | p. 295 |
| Acknowledgments | p. 295 |
| References | p. 295 |
| Epoxidation of Propylene with Oxygen-Hydrogen Mixtures | p. 297 |
| Introduction | p. 298 |
| Liquid-Phase Epoxidation of Propylene | p. 300 |
| Gas-Phase Epoxidation of Propylene | p. 301 |
| Conclusions | p. 310 |
| References | p. 311 |
| Propylene Epoxidation by O[subscript 2] + H[subscript 2] over Au Nanoparticles on Ti-Nanoporous Supports | p. 315 |
| Introduction | p. 316 |
| Propylene Epoxidation over Au/TS-1 Catalysts | p. 317 |
| Au on Ti-Containing Mesoporous Supports | p. 322 |
| Promoters and Postsynthesis Support Treatments | p. 324 |
| Reaction Kinetics | p. 327 |
| Conclusions and Future Outlook | p. 331 |
| Acknowledgments | p. 333 |
| References | p. 333 |
| The Epoxidation of Propene over Gold Nanoparticle Catalysts | p. 339 |
| Introduction | p. 340 |
| Experimental | p. 341 |
| Results and Discussion | p. 343 |
| Conclusions | p. 352 |
| Acknowledgments | p. 353 |
| References | p. 353 |
| Propylene Epoxidation via Shell's SMPO Process: 30 Years of Research and Operation | p. 355 |
| Introduction | p. 356 |
| Catalytic Epoxidation | p. 358 |
| SMPO Process Improvement | p. 363 |
| Conclusions | p. 369 |
| Acknowledgment | p. 369 |
| References | p. 369 |
| Propylene Epoxidation with Ethylbenzene Hydroperoxide over Ti-Containing Catalysts Prepared by Chemical Vapor Deposition | p. 373 |
| Introduction | p. 374 |
| Experimental | p. 375 |
| Results and Discussion | p. 376 |
| Conclusions | p. 385 |
| Acknowledgment | p. 385 |
| References | p. 385 |
| Metal Species Supported on Organic Polymers as Catalysts for the Epoxidation of Alkenes | p. 387 |
| Introduction | p. 388 |
| Supported Manganese Catalysts | p. 389 |
| Supported Molybdenum Catalysts | p. 396 |
| Supported Ruthenium and Iron Catalysts | p. 398 |
| Supported Titanium Catalysts | p. 399 |
| Supported Tungsten Catalysts | p. 400 |
| Supported Rhenium Catalysts | p. 401 |
| Supported Cobalt, Nickel, and Platinum Catalysts | p. 402 |
| Supported BINOL-Complexes of Lanthanoids and Calcium | p. 402 |
| Conclusion | p. 403 |
| Acknowledgment | p. 407 |
| References | p. 407 |
| Phase-Transfer Catalysis | p. 413 |
| Fine-Tuning and Recycling of Homogeneous Tungstate and Polytungstate Epoxidation Catalysts | p. 415 |
| Introduction | p. 416 |
| Characteristics and Preparation of Sandwich POMs | p. 417 |
| Benchmarking Sandwich POM-Catalyzed Epoxidations | p. 418 |
| Effect of Carboxylic Acids as Cocatalysts in Tungstate-Catalyzed Epoxidations | p. 420 |
| Epoxidations that Afford Acid-Sensitive Products | p. 421 |
| Sandwich POM Catalyst Recycling | p. 425 |
| Conclusions | p. 426 |
| Acknowledgments | p. 427 |
| References | p. 427 |
| Reaction-Controlled Phase-Transfer Catalysis for Epoxidation of Olefins | p. 429 |
| Introduction | p. 430 |
| Reaction-Controlled Phase-Transfer Catalyst Based on Quaternary Ammonium Phosphotungstates | p. 431 |
| Influence of the Composition of the Heteropolyphosphotungstate Anion [40] | p. 432 |
| Influence of Different Quaternary Ammonium Cations [43] | p. 433 |
| Epoxidation of Propylene with In Situ Generated H[subscript 2]O[subscript 2] as the Oxidant | p. 435 |
| Epoxidation of Propylene with Aqueous H[subscript 2]O[subscript 2] [45] as the Oxidant | p. 438 |
| Epoxidation of Cyclohexene and Others Olefins | p. 439 |
| Epoxidation of Allyl Chloride | p. 440 |
| Conclusion | p. 444 |
| Acknowledgments | p. 444 |
| References | p. 444 |
| Biomimetic Catalysis | p. 449 |
| Bio-Inspired Iron-Catalyzed Olefin Oxidations: Epoxidation Versus cis-Dihydroxylation | p. 451 |
| Introduction | p. 452 |
| Structure-Reactivity Correlation of Catalysts | p. 453 |
| Toward Synthetically Useful Applications | p. 457 |
| Mechanistic Landscape | p. 459 |
| Acknowledgment | p. 466 |
| References | p. 466 |
| Quantum Chemical Analysis of the Reaction Pathway for Styrene Epoxidation Catalyzed by Mn-Porphyrins | p. 471 |
| Introduction | p. 472 |
| Methodology | p. 473 |
| Results | p. 475 |
| Conclusions | p. 483 |
| Acknowledgments | p. 483 |
| References | p. 484 |
| Index | p. 487 |
| Table of Contents provided by Ingram. All Rights Reserved. |
An electronic version of this book is available through VitalSource.
This book is viewable on PC, Mac, iPhone, iPad, iPod Touch, and most smartphones.
By purchasing, you will be able to view this book online, as well as download it, for the chosen number of days.
Digital License
You are licensing a digital product for a set duration. Durations are set forth in the product description, with "Lifetime" typically meaning five (5) years of online access and permanent download to a supported device. All licenses are non-transferable.
More details can be found here.
A downloadable version of this book is available through the eCampus Reader or compatible Adobe readers.
Applications are available on iOS, Android, PC, Mac, and Windows Mobile platforms.
Please view the compatibility matrix prior to purchase.