| Description |
1 online resource (528 pages) |
| Contents |
880-01 Molecular Catalysts -- Contents -- List of Contributors -- Foreword -- Introduction -- Part I Mechanisms of Elementary Reactions in Catalytic Processes -- Chapter 1 Quantum Dynamics of Molecular Elementary Processes in Catalytic Transformations -- 1.1 Introduction -- 1.2 Structural and Energetic Aspects -- 1.3 Quantum Dynamical Calculations -- 1.3.1 Reaction Path Energy Profiles -- 1.3.2 Wave Packet Propagation for Late-Transition-Metal Complexes -- 1.3.3 Norm Decay and Lifetimes -- 1.3.4 Quantum Dynamics of Ethylene Insertion in Chromium Complexes -- 1.4 Summary and Outlook -- Acknowledgments -- References -- Chapter 2 Activation of Small Molecules with Metal and Metal Oxide Clusters in Inert Gas Matrixes -- 2.1 Introduction -- 2.2 The Matrix Isolation Technique -- Advantages and Limitations -- 2.2.1 Thermal Evaporation Versus Laser Ablation -- 2.2.2 Metal or CsI Substrates for the Matrix -- 2.3 Formation and Characterization of Metal Atom Dimers and Clusters -- 2.4 Reactions of Atom Dimers or Clusters -- 2.5 Formation and Characterization of Metal Oxides -- 2.6 Reactions Involving Metal Oxides -- 2.7 Concluding Remarks -- Acknowledgments -- References -- Chapter 3 Toward Single-Molecule Catalysis -- 3.1 Introduction -- 3.1.1 Single-Molecule Enzymology -- 3.1.2 Single-Molecule Studies in Chemistry -- 3.1.2.1 Single-Molecule Studies in Heterogeneous Catalysis -- 3.1.2.2 Single-Molecule Chemistry in Homogeneous Catalysis -- 3.2 Probes for Single-Molecule Chemistry -- 3.2.1 Fluorescence Properties: Overall Considerations -- 3.2.2 Fluorogenic Substrates -- 3.2.3 Substrates for Reversible Reactions -- 3.2.4 Substrates for Irreversible Reactions -- 3.3 Approaching Single-Molecule Studies in Homogeneous Catalysis -- 3.3.1 Fluorophore-Labeled Cu(II) Chelators and Substrates |
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880-01/(S 3.3.2 BODIPY Substrates for Probing Reactions of Double Bonds -- 3.4 Discussion and Perspectives -- Acknowledgments -- References -- Chapter 4 Intermediates and Elementary Reactions in Gold Catalysis -- 4.1 Introduction -- 4.2 The Initial Step: π-Coordination of the Substrate -- 4.3 The Nucleophilic Addition: Vinylgold and Alkylgold Intermediates -- 4.4 The Reaction of the Organogold Intermediates with Electrophiles -- 4.5 "Vinylidene" Gold(I) Intermediates -- 4.5.1 Setting the Stage -- 4.5.2 An Unexpected Regioselectivity Raises Questions -- 4.5.3 The Mechanistic Hypothesis -- 4.5.4 The Other Pathway -- 4.5.5 Gold Allenylidenes as Analogs of Gold Vinylidenes-- 4.5.6 Dual Activation Catalysts -- 4.6 Protons and Hydride in Gold Catalysis -- 4.7 Future Perspectives -- References -- Chapter 5 Diastereoselectivity in Alkene Metathesis -- 5.1 Introduction -- 5.2 Stereoselective Alkene Metathesis Catalysts -- 5.3 Combining Catalytic Activity and Stereoselectivity in Ruthenium Carbenes: an Antagonism-- 5.4 Stereoselectivity in Ring-Opening Metathesis Polymerization (ROMP) -- 5.5 Outlook -- 5.6 Summary -- References -- Part II New Catalysts -- New and Old Reactions -- Chapter 6 Oxidation Catalysis with High-Valent Nonheme Iron Complexes -- 6.1 Introduction -- 6.2 Bispidine Ligands -- 6.3 Oxidation of the Ferrous Precursors -- 6.4 Spin States of the Ferryl Catalysts -- 6.5 Redox Properties of the Ferryl Oxidants -- 6.6 Reactivity of the Ferryl Compounds -- 6.6.1 Olefine Oxidation -- 6.6.2 Alkane Oxidation -- 6.6.3 Sulfoxidation -- 6.6.4 Water Oxidation -- 6.6.5 Dioxygen as Oxidant -- 6.7 Conclusion -- Acknowledgment -- References -- Chapter 7 Single-Site Organochromium Catalysts for High Molecular Weight Polyolefins -- 7.1 Introduction -- 7.2 Ligand Design -- 7.3 Chromium Complexes of Non-Cp Ligands |
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7.3.1 Neutral Tridentate Ligands -- 7.3.2 Anionic Ligands -- 7.4 Chromium Complexes Based on Cp -- 7.4.1 Cp Systems with Covalently Bound Additional Donor Functions -- 7.5 Polymerization Behavior of Donor-Functionalized Cp Chromium Complexes Developed in Heidelberg -- 7.5.1 Structural Features -- 7.5.2 Catalyst Activation and Catalytic Activities -- 7.5.3 Chain Termination and Molecular Weights -- 7.6 En Route to Tunable Catalysts -- 7.7 Conclusion -- References -- Chapter 8 Ligand Design and Mechanistic Studies for Ni-Catalyzed Hydrocyanation and 2-Methyl-3-Butenenitrile Isomerization Based upon Rh-Hydroformylation Research -- 8.1 Introduction -- 8.2 Recent Advances in Ni-Catalyzed Hydrocyanation and Isomerization Reactions -- 8.2.1 Hydrocyanation of Vinylarenes -- 8.2.2 Hydrocyanation of 1,3-Dienes -- 8.2.3 Hydrocyanation of trans-3-Pentenenitrile -- 8.2.4 Isomerization of 2-Methyl-3-Butenenitrile -- 8.3 Recent Advances in Ni-Catalyzed Hydrocyanation and Isomerization Reactions Employing the TTP-Ligand Family -- 8.3.1 Genesis of the TTP-Ligand Family -- 8.3.2 Ni-Catalyzed Isomerization and Hydrocyanation with TTP-Type Phosphonite Ligands -- 8.3.3 Ni-Catalyzed Hydrocyanation Involving TTP-Type Phosphine Ligands -- 8.3.4 Applications and Mechanistic Studies of TTP-Type Phosphine Ligands in Ni-Catalyzed 2M3BN Isomerization -- Acknowledgments -- References -- Chapter 9 Strongly Electron Donating Tridentate N-Heterocyclic Biscarbene Ligands for Rhodium and Iridium Catalysts -- 9.1 Introduction -- 9.2 Ligand Systems -- 9.3 Synthesis and Reactivity of the Complexes -- 9.3.1 Synthesis of M(I) Complexes -- 9.3.2 Synthesis of M(III) Complexes -- 9.4 Catalytic Activities of the Rh Complexes -- 9.5 Catalytic Activities of the Ir Complexes -- 9.6 Discussion -- 9.7 Summary, Conclusion, and Outlook -- References |
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Chapter 10 NHCP Ligands for Catalysis -- 10.1 Introduction -- 10.2 Recent Advances in Catalysis with NHCP Ligands -- 10.2.1 Cross-Coupling Catalysis and Related Reactions -- 10.2.2 Miscellaneous Reactions -- 10.3 Recent Advances in Asymmetric Catalysis with Chiral NHCP Ligands -- 10.4 Recent Advances in NHCP Chemistry Featuring Bulky, Electron-Rich, Small-Bite-Angle Ligands -- 10.4.1 Ligand Synthesis of N-Phosphino- and N-Phosphinomethyl NHCs -- 10.4.2 N-Phosphino-NHC Transition-Metal Complexes -- 10.4.3 N-Phosphinomethyl-NHC Ruthenium Alkylidene Complexes -- References -- Part III Catalysts in Synthesis -- Chapter 11 Ir-Catalyzed Asymmetric Allylic Substitution Reactions -- Fundamentals and Applications in Natural Products Synthesis -- 11.1 Introduction -- 11.2 Background on Reaction Mechanism -- 11.3 Dibenzocyclooctatetraene (dbcot) as Ancillary Ligand -- 11.4 Applications in Organic Synthesis -- 11.4.1 Allylic Substitution in Combination with Ring Closing Metathesis -- 11.4.2 Domino-Hydroformylation-Cyclization (Hydroaminomethylation) -- 11.4.3 The Allylic Substitution in Combination with the Suzuki-Miyaura Reaction -- 11.4.4 Reactions of Enines Derived from Allylic Substitution Products -- 11.5 Conclusions -- Acknowledgments -- References -- Chapter 12 Sequential Catalysis Involving Metal-Catalyzed Cycloisomerizations and Cyclizations -- 12.1 Introduction -- 12.2 Sequences Initiated by Cycloisomerizations -- 12.2.1 Sequentially Pd-Catalyzed Sequences Initiated by Cycloisomerizations -- 12.2.2 Sequentially Rh-Catalyzed Sequences Initiated by Cycloisomerizations -- 12.3 Sequences Initiated by Ring-Closing Olefin Metathesis -- 12.3.1 Ring-Closing Metathesis-Isomerization Sequences -- 12.3.2 Ring-Closing Metathesis-Oxidation Sequences |
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12.4 Sequences Initiated by Alkynylation and Carbopalladative Insertions -- 12.5 Sequences Intercepted by Cyclizations -- 12.6 Conclusion -- Acknowledgment -- Abbreviations -- References -- Chapter 13 C-N-Coupling Reactions in Catalytic One-Pot Syntheses Using Molecular Group 4 Catalysts -- 13.1 Introduction -- 13.2 Group 4 Metal Catalysts for the Hydroamination and Hydrohydrazination of C-C Multiple Bonds as well as Complex Reaction Sequences Based Thereon -- 13.3 Case Histories -- 13.3.1 Highly Active Titanium Catalysts for the Hydrohydrazination of Terminal Alkynes and Aminoguanylation of Carbodiimides -- 13.3.2 A Zirconium-Catalyzed Non-Fischer-Type Pathway to Indoles -- References -- Chapter 14 Sequential Catalysis for the Stereoselective Synthesis of Complex Polyketides -- 14.1 Complex Polyketides -- 14.2 Domino Nucleophilic Addition-Tsuji-Trost Reaction -- 14.2.1 Concise Synthesis of Tetrahydropyrans by a Tandem oxa-Michael-Tsuji-Trost Reaction -- 14.2.2 Concise Synthesis of Acetal-Protected 1,3-syn-Diols by a Tandem Hemiacetal/Tsuji-Trost Reaction -- 14.2.3 General Concept and Further Applications for Diamine and Aminoalcohol Synthesis -- 14.3 Sequential Diyne Cyclization and Regioselective Opening of Zirconacyclopentadienes -- 14.4 Conclusion and Perspectives -- References -- Chapter 15 Modular Assembly of Chiral Catalysts with Polydentate Stereodirecting Ligands -- 15.1 Introduction -- 15.2 A Modular Synthesis of C3- and C1-Chiral 1,1,1-Tris(oxazolyl)ethanes ("Trisox") -- 15.2.1 C3-Chirality in Polymerization Catalysis with Rare-Earth Complexes |
| Summary |
Highlighting the key aspects and latest advances in the rapidly developing field of molecular catalysis, this book covers new strategies to investigate reaction mechanisms, the enhancement of the catalysts' selectivity and efficiency, as well as the rational design of well-defined molecular catalysts. The interdisciplinary author team with an excellent reputation within the community discusses experimental and theoretical studies, along with examples of improved catalysts, and their application in organic synthesis, biocatalysis, and supported organometallic catalysis. As a result, readers will gain a deeper understanding of the catalytic transformations, allowing them to adapt the knowledge to their own investigations. With its ideal combination of fundamental and applied research, this is an essential reference for researchers and graduate students both in academic institutions and in the chemical industry. With a foreword by Nobel laureate Roald Hoffmann |
| Bibliography |
Includes bibliographical references at the end of each chapters and index |
| Notes |
Print version record |
| Subject |
Catalysts -- Industrial applications
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Molecular structure.
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Molecular dynamics.
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molecular structure.
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SCIENCE -- Chemistry -- Physical & Theoretical.
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Catalysts -- Industrial applications
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Molecular dynamics
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Molecular structure
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| Form |
Electronic book
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| Author |
Hofmann, Peter
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| ISBN |
9783527673308 |
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352767330X |
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