Catalysis without Precious Metals E-Book

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

Seitenzahl: 498

Veröffentlichungsjahr: 2011

Beschreibung

Written for chemists in industry and academia, this ready reference and handbook summarizes recent progress in the development of new catalysts that do not require precious metals. The research thus presented points the way to how new catalysts may ultimately supplant the use of precious metals in some types of reactions, while highlighting the remaining challenges. An essential copanion for organic and catalytic chemists, as well as those working with/on organometallics and graduate students. From the contents: * Catalysis Involving the H' Transfer Reactions of First-Row Transition Metals * Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum Complexes * Molybdenum and Tungsten Catalysts for Hydrogenation, Hydrosilylation and Hydrolysis * Iron in Catalytic Alkene and Carbonyl Hydrogenation Reactions * Olefin Oligomerizations and Polymerizations Catalyzed by Iron and Cobalt Complexes * Cobalt and Nickel Catalyzed Reactions Involving C-H and C-N Activation Reactions * Development of Molecular Electrocatalysts for H2 Oxidation and Production Based on Inexpensive Metals * Nickel-Catalyzed Reductinve Couplings and Cyclizations * Copper-Catalyzed Ligand Promoted Ullmann-Type Coupling Reactions * Copper-Catalyzed Azide-Alkyne Cycloaddition * "Frustrated Lewis Pairs": A Metal-Free Strategy for Hydrogenation Catalysis

Leseprobe

Contents

Preface

List of Contributors

1 Catalysis Involving the H• Transfer Reactions of First-Row Transition Metals

1.1 H• Transfer Between M–H Bonds and Organic Radicals

1.2 H• Transfer Between Ligands and Organic Radicals

1.3 H• Transfer Between M–H and C–C Bonds

1.4 Chain Transfer Catalysis

1.5 Catalysis of Radical Cyclizations

1.6 Competing Methods for the Cyclization of Dienes

1.7 Summary and Conclusions

References

2 Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum

2.1 Introduction

2.2 Some Characteristics of Triamidoamine Complexes

2.3 Possible [HIPTN3N]Mo Intermediates in a Catalytic Reduction of Molecular Nitrogen

2.4 Interconversion of Mo(NH3) and Mo(N2)

2.5 Catalytic Reduction of Dinitrogen

2.6 MoH and Mo(H2)

2.7 Ligand and Metal Variations

2.8 Comments

Acknowledgements

References

3 Molybdenum and Tungsten Catalysts for Hydrogenation, Hydrosilylation and Hydrolysis

3.1 Introduction

3.2 Proton Transfer Reactions of Metal Hydrides

3.3 Hydride Transfer Reactions of Metal Hydrides

3.4 Stoichiometric Hydride Transfer Reactivity of Anionic Metal Hydride Complexes

3.5 Catalytic Hydrogenation of Ketones with Anionic Metal Hydrides

3.6 Ionic Hydrogenation of Ketones Using Metal Hydrides and Added Acid

3.7 Ionic Hydrogenations from Dihydrides: Delivery of the Proton and Hydride from One Metal

3.8 Catalytic Ionic Hydrogenations With Mo and W Catalysts

3.9 Mo Phosphine Catalysts With Improved Lifetimes

3.10 Tungsten Hydrogenation Catalysts with N-Heterocyclic Carbene Ligands

3.11 Catalysts for Hydrosilylation of Ketones

3.12 Cp2Mo Catalysts for Hydrolysis, Hydrogenations and Hydrations

3.13 Conclusion

Acknowledgements

References

4 Modern Alchemy: Replacing Precious Metals with Iron in Catalytic Alkene and Carbonyl Hydrogenation Reactions

4.1 Introduction

4.2 Alkene Hydrogenation

4.3 Carbonyl Hydrogenation

4.4 Outlook

References

5 Olefin Oligomerizations and Polymerizations Catalyzed by Iron and Cobalt Complexes Bearing Bis(imino)pyridine Ligands

5.1 Introduction

5.2 Precatalyst Synthesis

5.3 Precatalyst Activation and Catalysis

5.4 The Active Catalyst and Mechanism

5.5 Other Applications

5.6 Conclusions and Outlook

References

6 Cobalt and Nickel Catalyzed Reactions Involving C–H and C–N Activation Reactions

6.1 Introduction

6.2 Catalysis with Cobalt

6.3 Catalysis with Nickel

References

7 A Modular Approach to the Development of Molecular Electrocatalysts for H2 Oxidation and Production Based on Inexpensive Metals

7.1 Introduction

7.2 Concepts in Catalyst Design Based on Structural Studies of Hydrogenase Enzymes

7.3 A Layered or Modular Approach to Catalyst Design

7.4 Using the First Coordination Sphere to Control the Energies of Catalytic Intermediates

7.5 Using the Second Coordination Sphere to Control the Movement of Protons between the Metal and the Exterior of the Molecular Catalyst

7.6 Integration of the First and Second Coordination Spheres

7.7 Summary

Acknowledgements

References

8 Nickel-Catalyzed Reductive Couplings and Cyclizations

8.1 Introduction

8.2 Couplings of Alkynes with α,β-Unsaturated Carbonyls

8.3 Couplings of Alkynes with Aldehydes

8.4 Conclusions and Outlook

Acknowledgements

References

9 Copper-Catalyzed Ligand Promoted Ullmann-type Coupling Reactions

9.1 Introduction

9.2 C–N Bond Formation

9.3 C–O Bond Formation

9.4 C–C Bond Formation

9.5 C–S Bond Formation

9.6 C–P Bond Formation

9.7 Conclusion

References

10 Copper-Catalyzed Azide-Alkyne Cycloaddition (CuAAC)

10.1 Introduction

10.2 Azide–Alkyne Cycloaddition: Basics

10.3 Copper-Catalyzed Cycloadditions

Acknowledgements

References

11 “Frustrated Lewis Pairs”: A Metal-Free Strategy for Hydrogenation Catalysis

11.1 Phosphine-Borane Activation of H2

11.2 “Frustrated Lewis Pairs”

11.3 Metal-Free Catalytic Hydrogenation

11.4 Future Considerations

Acknowledgements

References

Index

Further Reading

Plietker, B. (Ed.)

Iron Catalysis in Organic Chemistry

Reactions and Applications

2008

Hardcover

ISBN: 978-3-527-31927-5

Jackson, S. D., Hargreaves, J. S. J. (Eds.)

Metal Oxide Catalysis

2008

Hardcover

ISBN: 978-3-527-31815-5

Drauz, K., Gröger, H., May, O. (Eds.)

Enzyme Catalysis in Organic Synthesis

2011

Hardcover

ISBN: 978-3-527-32547-4

Pihko, P. M. (Ed.)

Hydrogen Bonding in Organic Synthesis

2009

Hardcover

ISBN: 978-3-527-31895-7

Bäckvall, J.-E. (Ed.)

Modern Oxidation Methods

2011

Hardcover

ISBN: 978-3-527-32320-3

Mohr, F. (Ed.)

Gold Chemistry

Applications and Future Directions in the Life Sciences

2009

Hardcover

ISBN: 978-3-527-32086-8

Dupont, J, Pfeffer, M. (Eds.)

Palladacycles

Synthesis, Characterization and Applications

2008

Hardcover

ISBN: 978-3-527-31781-3

Sheldon, R. A., Arends, I., Hanefeld, U.

Green Chemistry and Catalysis

2007

Hardcover

ISBN: 978-3-527-30715-9

Dalko, P. I. (Ed.)

Enantioselective Organocatalysis

Reactions and Experimental Procedures

2007

Hardcover

ISBN: 978-3-527-31522-2

Cybulski, A., Moulijn, J. A., Stankiewicz, A. (Eds.)

Novel Concepts in Catalysis and Chemical Reactors

Improving the Efficiency for the Future

2010

Hardcover

ISBN: 978-3-527-32469-9

Yudin, A. K. (Eds.)

Catalyzed Carbon-Heteroatom Bond Formation

From Biomimetic Concepts to Applications in Asymmetric Synthesis

2011

Hardcover

ISBN: 978-3-527-32428-6

The Editor

Dr. R. Morris BullockPacific Northwest NationalLaboratoryP.O. Box 999, K2-57Richland, WA 99352USA

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

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ISBN: 978-3-527-32354-8

To Cindy, Claude and Lindsay

Preface

Many of the greatest success stories of organometallic and inorganic chemistry are in the application of metal complexes to catalytic reactions. In many cases, precious metals perform the heavy lifting, breaking H–H bonds, forming C– H or C–C bonds, etc. Precious metals have become so familiar in these roles that in some cases the precious metal and their catalytic reactivity seem almost inextricably linked. Wilkinson’s catalyst, a rhodium complex, played a pivotal role in our understanding of hydrogenations. More recently, Noyori and co - workers developed remarkably reactive ruthenium complexes for asymmetric catalytic hydrogenations of C=O bonds. Over 150 years have passed since the discovery of a fuel cell that oxidizes hydrogen, yet modern low - temperature fuel cells still require platinum. Many carbon - carbon coupling reactions used extensively in organic synthesis function efficiently with extremely low loadings of palladium catalysts.

Kicking old habits is never easy, despite the allure of significant rewards for making the desired change. Yet we now know that the use of precious metals in catalysis is not always required. The research presented in this book shows how new catalysts that do not require precious metals may ultimately supplant the use of precious metals in some types of reactions. This book also highlights the challenges remaining in the development of catalysts that do not require precious metals. The pathway to devising new types of catalysts using abundant metals often involves scrutiny of reaction mechanisms that could potentially accomplish the desired goal, and finding ways to coerce inexpensive, abundant metals into accomplishing that task. In many cases those mechanisms are altogether different from those used in traditional precious metal catalysts. As can be seen in different chapters in this book, some of the catalytic reactions that use cheap metals are already competitive with well - known reactions that use precious metals. Even in new catalysts that do not yet exhibit rates or lifetimes that compare favorably to long - established and well - optimized precious metal catalysts, fundamentally new reactivity patterns have been discovered, and new classes of catalysts have been developed. This book provides detailed information on many types of reactions that can be catalyzed without the need for precious metals. I hope that these chapters may inspire others to join in the pursuit of “cheap metals for noble tasks.”

Research on alternatives to precious metal catalysts has been growing rapidly in recent years, and expected to experience increased growth in the future. The most obvious reason for replacing precious metals is that they are very expensive, often costing more than 100 or 1000 times the cost of base metals. The high cost is obviously connected to the low abundance of these metals. High cost alone is not the only reason, however; in some cases specialized organic ligands (used in asymmetric catalysis, for example) cost more than the metal. Substantial costs are involved in industrial processes when recovery and recycle of the metal is required. Another attribute of avoiding precious metals is that some metals like iron have a minimal environmental and toxicological impact. Importantly, some large - scale uses in energy storage and conversion currently being considered would require large amounts of precious metals. In automotive transportation, for example, conversion to a “hydrogen economy” based entirely on fuel cells that require platinum would not be feasible, not only due to the high cost, but because there is not enough platinum available to accommodate such a huge scale of usage.

The order of the chapters in this book follows their order in periodic table, starting at the first row of group 6 (Norton’s chapter on chromium catalysts) and continuing to Group 6 metals molybdenum and tungsten. While most of the inexpensive, abundant metals are from the first row of the periodic table, molybdenum and tungsten (from the second and third row of the periodic table) are exceptions, as they are much less expensive than precious metals. Subsequent chapters focus on catalysis by iron (Group 8), cobalt (Group 9), nickel (Group 10) and copper (Group 11). The last chapter highlights new catalysts that have no transition metals at all, using the main group elements phosphorus and boron. The cover highlights the inexpensive, abundant metals that are discussed in this book, with those metals being highlighted in green, and the precious metals of low abundance and high cost being shown in red. Manganese is abundant and inexpensive, and offers appealing opportunities for development into catalytic reactions. But since no chapters in this book focus on Mn, so it was not shown in green on the cover.

This book focuses on homogeneous (molecular) catalysts. There is a need to replace precious metals used in heterogeneous catalysis as well, but that topic is beyond the scope of material that can be covered in one book.

I sincerely thank all of the authors of the chapters in this book. They contributed their expertise and time in the writing of their chapters, and gracefully put up with annoying e - mails and editorial suggestions from me. I appreciate the enthusiasm they share for developing the chemistry of abundant, inexpensive metals as attractive alternatives to precious metals. Paul Chirik and Jack Norton gave me very helpful advice in the planning of this book.

I am deeply indebted to many scientific colleagues who have influenced my thinking, and who helped teach me chemistry over the years. In particular, Carol Creutz (Brookhaven National Laboratory) and Dan DuBois (Pacific Northwest National Laboratory) have both been extremely generous with their time and patient with my questions. I thank my scientific mentors, Chuck Casey and Jack Norton, for invaluable advice on many topics for more than twenty - five years.

It was a pleasure to work with Dr. Heike Nöthe at Wiley - VCH, and with Dr. Manfred Köhl in the early stages of preparations and planning for this book.

I dedicate this book to my wife, Cindy, to my son, Claude, and to my daughter, Lindsay. I thank them for being immensely supportive, including times when I was in the lab or my office rather than at home.

June 2010

R. Morris Bullock

List of Contributors

Ryan D. Baxter

University of Michigan

Department of Chemistry

930 North University Avenue

Ann Arbor, MI 48109 - 1055

USA

Renee Becker

University of Rochester

Department of Chemistry

Rochester, NY 14627

USA

R. Morris Bullock

Pacific Northwest National Laboratory

Chemical and Materials Sciences

Division

P.O. Box 999

K2 - 57

Richland, WA 99352

USA

Paul J. Chirik

Cornell University

Department of Chemistry and Chemical Biology

Baker Laboratory

Ithaca, NY 14853

USA

Daniel L. DuBois

Pacific Northwest National Laboratory

Chemical and Materials Sciences

Division

Richland, WA 99352

USA

M. Rakowski DuBois

Pacific Northwest National Laboratory

Chemical and Materials Sciences

Division

Richland, WA 99352

USA

M. G. Finn

The Scripps Research Institute

Department of Chemistry

10550 North Torrey Pines Road

La Jolla, CA 92037

USA

Valery V. Fokin

The Scripps Research Institute

Department of Chemistry

10550 North Torrey Pines Road

La Jolla, CA 92037

USA

Vernon C. Gibson

Imperial College

Department of Chemistry

South Kensington Campus

London SW7 2AZ

UK

John Hartung

Columbia University

Department of Chemistry

3000 Broadway

New York, NY 10027

USA

Yongwen Jiang

Chinese Academy of Sciences

Shanghai Institute of Organic

Chemistry

State Key Laboratory of Bioorganic and Natural Products Chemistry

354 Fenglin Lu

Shanghai 200032

China

William D. Jones

University of Rochester

Department of Chemistry

Rochester, NY 14627

USA

Dawei Ma

Chinese Academy of Sciences

Shanghai Institute of Organic

Chemistry

State Key Laboratory of Bioorganic and Natural Products Chemistry

354 Fenglin Lu

Shanghai 200032

China

Hasnain A. Malik

University of Michigan

Department of Chemistry

930 North University Avenue

Ann Arbor, MI 48109 - 1055

USA

John Montgomery

University of Michigan

Department of Chemistry

930 North University Avenue

Ann Arbor, MI 48109 - 1055

USA

Jack R. Norton

Columbia University

Department of Chemistry

3000 Broadway

New York, NY 10027

USA

Richard R. Schrock

Massachusetts Institute of Technology

Department of Chemistry

Cambridge, MA 02139

USA

Gregory A. Solan

University of Leicester

Department of Chemistry

University Road

Leicester LE1 7RH

UK

Douglas W. Stephan

University of Toronto

Department of Chemistry

80 St. George St.

Toronto

Ontario

Canada M5S 3H6