Molecular Catalysts E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 825

Veröffentlichungsjahr: 2014

Beschreibung

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.

Leseprobe

Table of Contents

Cover

Related Titles

Title Page

Copyright

List of Contributors

Foreword

1 The Magic Force That Became a Science

2 It Should Go Off, Shouldn't It?

3 Incendiary Acts

4 Döbereiner's Feuerzeug

5 Geopolitics and Science

6 Chemistry in Culture

7 How Does Hydrogen Burn?

8 Knowing without Seeing

References

Introduction

I

II

III

IV

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

1.4 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

2.3 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

3.2 Probes for Single-Molecule Chemistry

3.3 Approaching Single-Molecule Studies in Homogeneous Catalysis

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

4.6 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

6.7 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

7.4 Chromium Complexes Based on Cp

7.5 Polymerization Behavior of Donor-Functionalized Cp Chromium Complexes Developed in Heidelberg

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

8.3 Recent Advances in Ni-Catalyzed Hydrocyanation and Isomerization Reactions Employing the TTP-Ligand Family

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

9.4 Catalytic Activities of the Rh Complexes

9.5 Catalytic Activities of the Ir Complexes

9.6 Discussion

9.7 Summary, Conclusion, and Outlook

References

Chapter 10: NHCP Ligands for Catalysis

10.1 Introduction

10.2 Recent Advances in Catalysis with NHCP Ligands

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

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

11.5 Conclusions

Acknowledgments

References

Chapter 12: Sequential Catalysis Involving Metal-Catalyzed Cycloisomerizations and Cyclizations

12.1 Introduction

12.2 Sequences Initiated by Cycloisomerizations

12.3 Sequences Initiated by Ring-Closing Olefin Metathesis

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

References

Chapter 14: Sequential Catalysis for the Stereoselective Synthesis of Complex Polyketides

14.1 Complex Polyketides

14.2 Domino Nucleophilic Addition–Tsuji–Trost Reaction

14.3 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

C

3

- and

C

1

-Chiral 1,1,1-Tris(oxazolyl)ethanes (“Trisox”)

15.3 The

Boxmi

Pincer System: a Highly Efficient Modular Stereodirecting Ligand for a Broad Range of Catalytic Reactions

15.4 Bidentate N-Heterocyclic Carbene Ligands Incorporating Oxazoline Units

15.5 New Modular Di- and Tridentate Phospholane Ligands

References

Part IV: Structures and Mechanisms in Biological Systems

Chapter 16: Beating and Employing X-Ray-Induced Radiation Damage in Structural Studies of Hemoproteins

16.1 Introduction

16.2 Cytochrome P450 Enzymes

16.3 Photoelectrons – Friend and Foe

16.4 X-ray Free-Electron Lasers

References

Chapter 17: The Catalytic Strategy of P–O Bond-Cleaving Enzymes: Comparing EcoRV and Myosin

17.1 Introduction

17.2 Results

17.3 Conclusions

17.4 Methods

References

Chapter 18: Selective Hybrid Catalysts Based on Nucleic Acids

18.1 Introduction

18.2 Hybrid Catalysis

18.3 DNA-Based Hybrid Catalysis

18.4 Organometallic Chemistry with Nucleic Acids

18.5 Combinatorial Selections of Catalysts from Nucleic Acid Libraries

18.6 Site-Specific Internal Functionalization of Nucleic Acids with Transition-Metal Ligands and Other Moieties

18.7 Metallation of DNA–Ligand Conjugates

18.8 Site-Specific Terminal Functionalization of Nucleic Acids with Substrates

18.9 Allylic Aminations by DNA-Based Hybrid Catalysts

18.10 Summary and Outlook

References

Part V: Studies of Immobilized Catalysts – Introduction

V.1 Introduction

V.2 Covalent Immobilization of Catalysts

V.3 Support Materials

V.4 Examples of Immobilized Catalyst Systems

References

Chapter 19: Dendrimers as Platforms for Stereoselective Catalysis

19.1 Introduction

19.2 Fixation of Chiral Catalysts on Dendrimers and Hyperbranched Polymers

19.3 Case Histories

19.4 Conclusion and Outlook

References

Chapter 20: Solid Phases as Protective Environments for Biomimetic Catalysts

20.1 Introduction

20.2 Site Isolation Experienced by Matrix-Bound Transition-Metal Complexes

20.3 Immobilized Structural and Spectroscopic Active Site Models

20.4 Elementary Reaction Steps Performed by Solid-Phase Supported Complexes

20.5 Immobilized Functional Active Site Models

20.6 Final Remarks

Abbreviations

References

Chapter 21: High-Throughput Screening of Catalysts and Reactions

21.1 Introduction

21.2 Technical Requirements for On-Column Reaction Chromatography

21.3 Determination of Kinetic Data

21.4 Determination of Activation Parameters

21.5 On-Column Reaction Chromatography for the Investigation of Catalytic Reactions

21.6 Outlook

References

Index

End User License Agreement

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Guide

Cover

Table of Contents

Foreword

Introduction

Part I: Mechanisms of Elementary Reactions in Catalytic Processes

Chapter 1: Quantum Dynamics of Molecular Elementary Processes in Catalytic Transformations

List of Illustrations

Figure 1

Figure 2

Figure 3

Scheme 1.1

Scheme 1.2

Figure 1.1

Figure 1.2

Figure 1.3

Figure 1.4

Figure 1.5

Figure 1.6

Figure 1.7

Figure 1.8

Figure 1.9

Figure 1.10

Figure 1.11

Figure 2.1

Figure 2.2

Figure 2.3

Figure 2.4

Scheme 2.1

Scheme 2.2

Figure 2.5

Figure 2.6

Figure 2.7

Figure 2.8

Figure 2.9

Figure 2.10

Figure 3.1

Figure 3.2

Figure 3.3

Figure 3.4

Figure 3.5

Figure 3.6

Figure 3.7

Figure 3.8

Figure 3.9

Figure 3.10

Figure 3.11

Scheme 4.1

Figure 4.2

Figure 4.1

Scheme 4.2

Scheme 4.3

Scheme 4.4

Scheme 4.5

Scheme 4.6

Scheme 4.7

Figure 4.3

Scheme 4.8

Scheme 4.9

Scheme 4.10

Scheme 4.11

Figure 4.4

Scheme 4.12

Scheme 4.13

Scheme 4.14

Scheme 4.15

Scheme 4.16

Scheme 4.17

Scheme 4.18

Scheme 4.19

Scheme 4.20

Scheme 4.21

Scheme 5.1

Figure 5.1

Scheme 5.2

Scheme 5.3

Scheme 5.4

Scheme 5.5

Scheme 5.6

Scheme 5.7

Scheme 5.8

Figure 5.2

Scheme 5.9

Scheme 5.10

Scheme 5.11

Figure 5.3

Scheme 5.12

Scheme 5.13

Scheme 5.14

Scheme 5.15

Scheme 6.1

Figure 6.1

Scheme 6.2

Figure 6.2

Figure 6.3

Scheme 6.3

Scheme 6.4

Scheme 6.5

Scheme 6.6

Figure 6.4

Figure 7.1

Figure 7.2

Figure 7.3

Figure 7.4

Figure 7.5

Figure 7.6

Figure 7.7

Scheme 8.1

Scheme 8.2

Scheme 8.3

Scheme 8.4

Scheme 8.5

Scheme 8.6

Scheme 8.7

Scheme 8.8

Figure 8.1

Figure 8.2

Figure 8.3

Scheme 8.9

Scheme 8.10

Figure 8.4

Scheme 8.11

Scheme 8.12

Figure 9.1

Figure 9.2

Figure 9.3

Figure 9.4

Scheme 9.2

Scheme 9.1

Scheme 9.3

Scheme 9.4

Scheme 9.5

Scheme 9.6

Scheme 9.7

Scheme 9.8

Figure 9.5

Figure 9.6

Figure 9.7

Figure 9.8

Figure 9.9

Figure 9.10

Figure 9.11

Figure 9.12

Figure 9.13

Figure 9.14

Figure 10.1

Scheme 10.1

Scheme 10.2

Scheme 10.3

Scheme 10.4

Figure 10.2

Scheme 10.5

Figure 10.3

Scheme 10.6

Figure 10.4

Figure 10.5

Scheme 10.7

Scheme 10.8

Scheme 10.9

Scheme 10.10

Scheme 10.11

Scheme 10.12

Scheme 10.13

Scheme 10.14

Scheme 11.1

Scheme 11.2

Scheme 11.3

Figure 11.1

Figure 11.2

Scheme 11.4

Scheme 11.5

Scheme 11.6

Scheme 11.7

Scheme 11.8

Figure 11.3

Scheme 11.9

Scheme 11.10

Scheme 11.11

Scheme 11.12

Scheme 11.13

Schemes 11.14

Figure 11.15

Scheme 11.16

Scheme 12.1

Scheme 12.2

Scheme 12.3

Scheme 12.4

Scheme 12.5

Scheme 12.6

Scheme 12.7

Scheme 12.8

Scheme 12.9

Scheme 12.10

Scheme 12.11

Scheme 12.12

Scheme 12.13

Scheme 12.14

Scheme 12.15

Scheme 12.16

Scheme 12.17

Scheme 12.18

Scheme 12.19

Scheme 12.20

Scheme 12.21

Scheme 12.22

Scheme 12.23

Scheme 12.24

Scheme 12.25

Scheme 12.26

Scheme 12.27

Scheme 12.28

Scheme 12.29

Scheme 13.1

Scheme 13.2

Scheme 13.3

Scheme 13.4

Scheme 13.5

Figure 13.1

Scheme 13.6

Scheme 13.7

Scheme 13.8

Scheme 13.9

Figure 13.2

Figure 13.3

Scheme 13.10

Scheme 13.11

Figure 13.4

Figure 13.5

Figure 14.1

Scheme 14.1

Scheme 14.2

Scheme 14.3

Scheme 14.4

Scheme 14.5

Scheme 14.6

Scheme 14.7

Scheme 14.8

Scheme 14.9

Scheme 14.10

Scheme 14.11

Scheme 14.12

Figure 15.1

Scheme 15.1

Scheme 15.2

Scheme 15.3

Figure 15.2

Scheme 15.4

Scheme 15.5

Figure 15.3

Scheme 15.6

Scheme 15.7

Scheme 15.8

Scheme 15.9

Scheme 15.10

Scheme 15.11

Scheme 15.12

Scheme 15.13

Scheme 15.14

Scheme 15.15

Figure 15.4

Figure 15.5

Scheme 15.16

Figure 15.6

Scheme 15.17

Figure 15.7

Scheme 15.18

Scheme 15.19

Figure 15.8

Figure 16.1

Figure 16.2

Figure 16.3

Figure 17.1

Figure 17.2

Figure 17.3

Figure 17.4

Figure 17.5

Figure 17.6

Figure 17.7

Figure 18.1

Figure 18.2

Figure 18.3

Scheme 18.1

Figure 18.4

Figure 18.5

Figure 18.6

Figure 18.7

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 19.1

Scheme 19.1

Scheme 19.2

Figure 19.2

Figure 19.3

Scheme 19.3

Figure 19.4

Scheme 19.4

Figure 19.5

Figure 19.6

Scheme 19.5

Scheme 19.6

Figure 19.7

Figure 19.8

Figure 19.9

Figure 20.1

Figure 20.2

Figure 20.3

Figure 20.4

Figure 20.5

Figure 20.6

Figure 20.7

Figure 20.8

Figure 20.9

Figure 20.10

Figure 20.11

Figure 20.12

Figure 20.13

Figure 21.1

Figure 21.2

Figure 21.3

Figure 21.4

Figure 21.5

Figure 21.6

Figure 21.7

Figure 21.8

Scheme 21.1

Figure 21.9

Figure 21.10

Figure 21.11

Figure 21.12

Scheme 21.2

Figure 21.13

List of Tables

Table 5.1

Table 6.1

Table 6.2

Table 6.3

Table 8.1

Table 8.2

Table 10.1

Table 10.2

Table 15.1

Table 15.2

Table 15.3

Table 15.4

Table 15.5

Table V.1

Table 19.1

Table 19.2

Table 21.1

Table 21.2

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Edited by Lutz H. Gade and Peter Hofmann

Molecular Catalysts

Structure and Functional Design

The Editors

Prof. Dr. Lutz H. Gade

Ruprecht-Karls-Universität Heidelberg

Anorganisch-Chem. Institut (ACI)

Im Neuenheimer Feld 270

69120 Heidelberg

Germany

Prof. Dr. Peter Hofmann

Ruprecht-Karls-Universität Heidelberg

Organisch-Chemisches Institut (OCI)

Im Neuenheimer Feld 270

69120 Heidelberg

Germany

Cover picture

Source: BASF Pressefoto

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List of Contributors

Marcel Brill

Ruprecht-Karls-Universität Heidelberg

Organisch-Chemisches Institut (OCI)

Im Neuenheimer Feld 270

Heidelberg

Germany

Dominik Brox

Ruprecht-Karls-Universität Heidelberg

Physikalisch-Chemisches Institut (PCI)

Im Neuenheimer Feld 229

Heidelberg

Germany

Peter Comba

Ruprecht-Karls-Universität Heidelberg

Anorganisch-Chemisches Institut (ACI)

Im Neuenheimer Feld 270

Heidelberg

Germany

Thomas Debnar

Rheinische Friedrich-Wilhelms-University of Bonn

Department of Organic Chemistry and Biochemistry

Gerhard-Domagk-Street 1

Bonn

Germany

Markus Enders

Ruprecht-Karls Universität Heidelberg

Anorganisch-Chemisches Institut (ACI)

Im Neuenheimer Feld 270