Advances in Organometallic Chemistry and Catalysis E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1562

Veröffentlichungsjahr: 2013

Beschreibung

A contemporary compilation of recent achievements in organometallic chemistry The prestigious International Conference on Organometallic Chemistry (ICOMC) was launched in 1963, providing a forum for researchers from around the world to share their findings and explore new paths to advance our knowledge and application of organometallic chemistry. The 25th ICOMC, held in Lisbon in 2012, gathered more than 1,200 participants from 54 countries. This volume celebrates the 25th Silver Edition and the 50th Gold Year of the ICOMC. Featuring contributions from invited 25th ICOMC speakers, Advances in Organometallic Chemistry and Catalysis highlights recent achievements and new and emerging areas of research in the field. Its seven sections cover: * Activation and Functionalization of Carbon Single Bonds and Small Molecules * Organometallic Synthesis and Catalysis * Organometallic Polymerization Catalysis * Organometallic Polymers and Materials * Organometallic Chemistry and Sustainable Energy * Bioorganometallic Chemistry * Organometallic Electrochemistry Chapters discuss fundamental underlying concepts, offer illustrative examples and cases, and explore future avenues for continued research. Readers will discover basic principles and properties of organometallic compounds, reaction mechanisms, and detailed descriptions of current applications. Collectively, these chapters underscore the versatility, richness, and potential of modern organometallic chemistry, including its interrelationships with other scientific disciplines. All the contributions are extensively referenced, providing a gateway to the most important original research papers and reviews in organometallic chemistry. Presenting a contemporary understanding of organometallic chemistry and its many applications, Advances in Organometallic Chemistry and Catalysis is recommended for all researchers in the field, from students to advanced investigators.

Leseprobe

Table of Contents

Title Page

Copyright

Preface

1.1 Organometallic Chemistry, The Science And Applications

1.2 This Book and The International Conferences on Organometallic Chemistry (ICOMC)

Reference

Contributors

Part I: Activation and Functionalization of Carbon Single Bonds and of Small Molecules

Chapter 1: Organometallic Complexes as Catalysts in Oxidation of C–H Compounds

1.1 Introduction

1.2 Oxygenation Reactions with Oxidants other than Peroxides

1.3 Oxygenation of C–H Bonds with Peroxides

1.4 Conclusions and Outlook

Acknowledgment

References

Chapter 2: Toward Functionalization of Alkanes Under Environmentally Benign Conditions

2.1 Introduction

2.2 Peroxidative Oxidations of Alkanes to Alcohols and Ketones, Catalyzed by Transition Metal Complexes

2.3 Metal-Free Alkane Hydrocarboxylation and Related Carboxylation

2.4 Final Remarks

Acknowledgment

References

Chapter 3: Self-Assembled Multicopper Complexes and Coordination Polymers for Oxidation and Hydrocarboxylation of Alkanes

3.1 Introduction

3.2 Self-Assembly Synthesis in Aqueous Medium

3.3 Aminoalcoholate Multicopper Complexes and Coordination Polymers

3.4 Application in Alkane Oxidation

3.5 Application in Alkane Hydrocarboxylation

3.6 Concluding Remarks

Acknowledgments

References

Chapter 4: Activation of C–O and C–F Bonds by Pincer–Iridium Complexes

4.1 Introduction

4.2 Cleavage and Oxidative Addition Of C–O Bonds

4.3 Cleavage and Oxidative Addition of C–F Bonds

4.4 Summary

Acknowledgments

References

Chapter 5: Functionalization of sp2 and sp3 Carbon Centers Catalyzed by Polyoxometalates and Metalloporphyrins

5.1 Introduction

5.2 Functionalization of Carbon Centers Under Homogeneous Conditions

5.3 Functionalization of sp2 Carbon Centers Under Homogeneous Conditions

5.4 Functionalization of sp2 and sp3 Carbon Centers Under Heterogeneous Conditions

5.5 Final Remarks

Acknowledgments

References

Chapter 6: Quasi-Borinium Cation Based on Cobalt Bis(Dicarbollide): Its Lewis Acidity and C–H and C–X Bond Activation

6.1 Introduction

6.2 Quasi-Borinium Cations: Formation and Reactivity

6.3 C–H Activation of Arenes

6.4 C–X Activation of Halogen Alkanes

6.5 Lewis Acidity of Quasi-Borinium Cation

References

Chapter 7: Transition-Metal-Promoted Functionalization of Carboranes

7.1 Introduction

7.2 [2 + 2 + 2] Cycloaddition of Ni–Carboryne with Alkynes

7.3 Coupling Reaction of Ni–Carboryne with Alkenes

7.4 [2 + 2 + 2] Cycloaddition of Ni–Carboryne with Activated Alkenes and Alkynes

7.5 Ni-Catalyzed [2 + 2 + 2] Cycloaddition of Carboryne with Alkynes

7.6 Pd/Ni-Cocatalyzed [2 + 2 + 2] Cycloaddition of 1,3-Dehydro-o-Carborane with Alkynes

7.7 Reaction of Zirconocene–Carboryne with Polar Unsaturated Molecules

7.8 Reaction of Zirconocene–Carboryne with Pyridines

7.9 Reaction of Zirconocene–Carboryne with Alkynes and Alkenes

7.10 Zr/Ni CO-Mediated [2 + 2 + 2] Cycloaddition of Carboryne with Two Different Alkynes

7.11 Zr/Ni CO-Mediated [2 + 2 + 2] Cycloaddition of Carboryne with Unactivated Alkenes and Alkynes

7.12 Conclusions and Perspectives

Acknowledgment

References

Chapter 8: Weak Interactions and M–H Bond Activation

8.1 Introduction

8.2 Metal Hydrides in Hydrogen Bonding

8.3 Hydrogen Bonding and Proton Transfer

8.4 Activation of H2 in the Metal Coordination Sphere

8.5 Conclusions

Acknowledgment

References

Part II: Organometallic Synthesis and Catalysis

Chapter 9: Complexes with Protic N-Heterocyclic Carbene (NR,NH-NHC) Ligands

9.1 Introduction

9.2 Complexes With NR,NH- and NH,NH-NHCS from Cyclic Ligand Precursors

9.3 Complexes with NR,NH- and NH,NH-NHCs by Template-Controlled Cyclization Reactions

9.4 Complexes with NR,NH-NHCs by Oxidative Addition of Azoles

9.5 Conclusion

Acknowledgment

References

Chapter 10: Cyclopentadienyl-Functionalized N-Heterocyclic Carbene Complexes of Iron and Nickel: Catalysts for Reductions

10.1 Introduction

10.2 Preparation of Cyclopentadienyl-Functionalized N-Heterocyclic Carbene Ligands

10.3 Cyclopentadienyl-Functionalized N-Heterocyclic Carbene Complexes of Iron and Nickel

10.4 Half-Sandwich Iron and Nickel NHC Complexes as Catalysts for Reductions

References

Chapter 11: Palladium-(Acyclic Diaminocarbene) Species as Alternative to Palladium-(Nitrogen Heterocyclic Carbenes) in Cross-Coupling Catalysis

11.1 Introduction

11.2 Synthetic Approaches to Palladium Complexes Bearing ADC Ligands

11.3 Catalytic Applications of Palladium-(ADC)s

11.4 Final Remarks

Acknowledgments

References

Chapter 12: Synthesis of Metallocenes Via Metathesis in Metal Coordination Spheres

12.1 Introduction

12.2 Polymers Bearing Metallocene Moieties by Ring-Opening Metathesis Polymerization or Acyclic Diene Metathesis Polymerization

12.3 Synthesis of Metallocenes by Ring-Closing Metathesis

12.4 Synthesis of Metallocenes by Cross-Metathesis

12.5 Conclusions and Outlook

References

Chapter 13: 13

13.1 Introduction

13.2 Metal-Mediated [2 + 3] Dipolar Cycloaddition to Nitriles and Isocyanides: Synthetic Studies

13.3 Metal-Mediated [2 + 3] Cycloaddition to Nitriles and Isocyanides: Theoretical Studies

13.4 Final Remarks

Acknowledgment

References

Chapter 14: Coordination Chemistry of Oxazoline/Thiazoline-Based P,N Ligands

14.1 Definition of Polyfunctional Ligands

14.2 P,N-Chelating Ligands Based on Oxazoline/Thiazoline SYSTEM

Summary

Acknowledgments

References

Chapter 15: “Click” Copper Catalyzed Azide–Alkyne Cycloaddition (CuAAC) in Aqueous Medium

15.1 Introduction

15.2 CuAAC: Organic Solvents Versus Aqueous Media

15.3 Final Remarks

Acknowledgments

References

Chapter 16: Organogold Catalysis: Homogeneous Gold-Catalyzed Transformations for a Golden Jubilee

16.1 Introduction

16.2 Electrophilic Gold Species: Principle and Main Modes of Reactivity

16.3 Gold Catalysts

16.4 Gold-Catalyzed Activation of Multiple Carbon–Carbon Bonds: Functionalization by Addition of Oxygen, Nitrogen, Sulfur, or Carbon Nucleophiles

16.5 Intermolecular Trapping of Reactive Organogold Intermediates

16.6 Oxene and Nitrene Precursors as Nucleophiles

16.7 Coupling Reactions

16.8 Generation of Structural Complexity

16.9 Asymmetric Catalysis

16.10 Gold Catalysis and Total Synthesis

16.11 Conclusion

References

Chapter 17: Vanadium(IV) Complexes Derived from Aromatic o-Hydroxyaldehydes and Tyrosine Derivatives: Catalytic Evaluation in Sulfoxidations

17.1 Introduction

17.2 Results and Discussion

17.3 Conclusions

Acknowledgments

References

Chapter 18: Microwave-Assisted Catalytic Oxidation of Alcohols to Carbonyl Compounds

18.1 Introduction

18.2 Homogeneous Catalysis

18.3 Heterogeneous Catalysis

18.4 Conclusions

References

Chapter 19: Oxidation of Glycerol with Hydrogen Peroxide Catalyzed by Metal Complexes

19.1 Introduction

19.2 Glycerol Oxidation with H2O2 Catalyzed by the O3(CO)12/Pyridine Combination

19.3 Oxidation of Glycerol with H2O2 Catalyzed by Soluble Complex [LMn(O)3MnL](PF6)2 and its Heterogenized form [LMn(O)3MnL]2[SiW12O40]

19.4 Oxidation of Glycerol with TBHP or H2O2 Catalyzed by Water-Soluble Tetracopper(II) Triethanolaminate Copper Complex

19.5 Conclusions

Acknowledgment

References

Chapter 20: Involvement of an Acetato Ligand in the Reductive Elimination Step of the Rhodium-Catalyzed Methanol Carbonylation

20.1 Introduction

20.2 NMR and Infrared High Pressure Studies and DFT Calculations

20.3 Conclusion

References

Chapter 21: Half-Sandwich Rhodium(III), Iridium(III), and Ruthenium(II) Complexes with Ancillary Pyrazole-Based Ligands

21.1 Introduction

21.2 Half-Sandwich R(II) Derivatives

21.3 Half-Sandwich R(III) and I(III) Derivatives

21.4 Half-Sandwich Derivatives with Acylpyrazolone Ligands

21.5 Conclusions and Perspectives

References

Chapter 22: Carbon–Scorpionate Complexes in Oxidation Catalysis

22.1 Introduction

22.2 Peroxidative Oxygenations of Alkanes

22.3 Oxidation of Alkanes by Molecular Oxygen

22.4 Carboxylation of Light Alkanes

22.5 Baeyer–Villiger Oxidation of Ketones

22.6 Final Remarks

Acknowledgment

References

Chapter 23: Toward Chemoselective Bioconjugative Desulfitative Catalysis

23.1 Introduction

23.2 Thioorganic-Boronic Acid Desulfitative Cross-Coupling

23.3 Cu-Catalyzed Desulfitative Coupling

23.4 Conclusion: Approaching Aqueous Desulfitative Reaction Conditions for Biological Applications

References

Chapter 24: Sulfoxide Redox Chemistry with Molybdenum Catalysts

24.1 Introduction

24.2 Results and Discussion

24.3 Conclusions

24.4 Computational details

Acknowledgment

References

Chapter 25: A New Family of Zirconium Complexes Anchored by Dianionic Cyclam-Based Ligands: Syntheses, Structures, and Catalytic Applications

25.1 Introduction

25.2 Syntheses and Molecular Structures

25.3 Thermaly Induced Orthometallation and Intramolecular Hydroamination of Aminoalkenes

25.4 ROP of Lactide and Cyclam Functionalization

25.5 Concluding Remarks

25.6 Aknowledgment

References

Chapter 26: Metal–Organo Multicatalysis: An Emerging Concept

26.1 Introduction

26.2 Cooperative Catalysis

26.3 Amines as catalysts

26.4 N-Heterocyclic Carbenes as Organocatalysts

26.5 Brønsted Acids as Organocatalysts

26.6 Relay and Sequential Catalysis

26.7 N-Heterocyclic Carbenes as Organocatalysts

26.8 Brønsted Acids as Organocatalysts

26.9 Conclusion

References

Part III: Organometallic Polymerization Catalysis

Chapter 27: Coordinative Chain Transfer Polymerization and Copolymerization by Means of Rare Earth Organometallic Catalysts for the Synthesis of Tailor-Made Polymers

27.1 Introduction

27.2 Basic Concepts

27.3 Catalytic Systems and Their Applications in Coordinative Chain Transfer Polymerization

27.4 Catalytic Systems and Their Applications in Coordinative Chain Transfer Copolymerization (CCTcoP)

27.5 Discussion

27.6 Conclusion—Perspectives

References

Chapter 28: Charge-Neutral and Cationic Complexes of Large Alkaline Earths for Ring-Opening Polymerization and Fine Chemicals Catalysis

28.1 Synthesis of Charge-Neutral Heteroleptic Ring-Opening Polymerization Catalysts Based on Large Alkaline Earths

28.2 Synthesis of Well-Defined, Solvent-Free Cationic Complexes of the Large Alkaline Earths

28.3 Immortal Ring-Opening Polymerizations of Cyclic Esters Catalyzed by Single-Site Alkaline Earth Catalysts

28.4 Intermolecular Hydroamination of Activated Alkenes Catalyzed By Charge-Neutral Heteroleptic Complexes of Large Alkaline Earths

28.5 Intermolecular Hydrophosphination of Styrene Catalyzed by Charge-Neutral Heteroleptic Complexes of Large Alkaline Earths

28.6 Hydrophosphonylation of Aldehydes and Nonactivated Ketones by Charge-Neutral Homoleptic And Heteroleptic Complexes of Large Alkaline Earths

Acknowledgments

References

Part IV: Organometallic Polymers and Materials

Chapter 29: Organometallic Polymers

29.1 Introduction

29.2 Metal-Backbone Organometallic Polymers

29.3 Metallic-Side Organometallic Polymers

29.4 Summary and Conclusions

Acknowledgements

References

Chapter 30: From Serendipity to Porosity:Synthesis and Reactivity of Coordination Polymers Based on Copper Trinuclear Triangular Motifs

30.1 Introduction

30.2 Coordination Polymers

30.3 Trinuclear Triangular CuII Moieties to Build CPs

30.4 Cu(pz)2-Based Coordination Polymers. A Case of “Porosity Without Pores”

30.5 Concluding Remarks

Acknowledgments

Dedication

References

Chapter 31: Organometallic Nanoparticles

31.1 Introduction

31.2 Ruthenium

31.3 Ligand-Stabilized Ruthenium Nanoparticles

31.4 Iron

31.5 Cobalt

31.6 Conclusion

Acknowledgments

References

Chapter 32: Organometallic Compounds in the Synthesis of New Materials: Old Ligands, New Tricks

32.1 Introduction

32.2 Functionalized Alcohols as Ligands

32.3 Organometallics in the Synthesis of Heterometallic Complexes

32.4 Conclusions

Acknowledgments

References

Chapter 33: The Role of Organometallic Complexes in the Synthesis of Shaped Carbon Materials

33.1 Introduction

33.2 General Comments

33.3 The Shapes Taken by Carbon

33.4 The Catalyst–Carbon Interaction

33.5 Mechanism of Carbon Growth from a Metal Particle

33.6 Organometallic Catalysts and Carbon Synthesis

33.7 Conclusion

Acknowledgments

References

Chapter 34: Metal Catalysis in Fullerene Chemistry

34.1 Introduction to Fullerenes

34.2 General Remarks on the Chemical Reactivity of Fullerenes

34.3 Metal-Mediated Reactions in Fullerene Chemistry

34.4 Asymmetric Catalysis in Fullerene Chemistry

34.5 Conclusions

References

Chapter 35: Organometallic Complexes of Sumanene

35.1 Introduction

35.2 Organolithium Complexes of Sumanene

35.3 η6-Coordination Complexes of Sumanene

35.4 Concluding Remarks and Future Prospects

Acknowledgements

References

Chapter 36: Advances in Luminescent Tetracoordinate Organoboron Compounds

36.1 Introduction

36.2 Luminescent Tetracoordinate Organoboron Compounds

36.3 Applications

36.4 Conclusions

Acknowledgment

References

Chapter 37: Mechanochemistry: A Tool in the Synthesis of Catalysts, Metallodrugs, and Metallopharmaceuticals

37.1 Introduction

37.2 Mechanochemistry in Supramolecular Synthesis

37.3 Mechanochemistry in Organic and Coordination Synthesis

37.4 Mechanochemistry in Metallopharmaceuticals and Metallodrugs

37.5 Mechanochemistry in Catalysis and Catalysts

37.6 Conclusions

References

Part V: Organometallic Chemistry and Sustainable Energy

Chapter 38: Organometallic Compounds for Dye-Sensitized Solar Cells (DSSC)

38.1 Introduction

38.2 Ruthenium Complexes for DSSC

38.3 Non-Ruthenium Metal Complexes for DSSC

38.4 Structure of Metal Complex Sensitizers

38.5 Performance Evaluation of Dye-Sensitized Solar Cells

38.6 Research Development on Metal Complexes for Dye-Sensitized Solar Cells

38.7 THE INTERACTION AND THE BINDING MODE OF DYES ON TiO2 SURFACE

38.8 Metal Complexes as Redox Mediators for DSSC

38.9 Conclusion

References

Chapter 39: Synthetic Photosynthesis for the Conversion of Large Volumes of Carbon Dioxide into Energy-Rich Molecules: Saving Fossil Fuels by Recycling Carbon

39.1 Introduction

39.2 The Past

39.3 The Present

39.4 The Future: Synthetic Photosynthesis

39.5 Concluding Remarks

References

Chapter 40: Ionic Liquids for Hydrogen Storage: Opportunities for Organometallic Chemistry

40.1 Introduction

40.2 Ionic Liquids

40.3 Hydrogen Storage Materials: Hydrogen-Rich Molecules

40.4 Hydrogen Storage Systems Involving Ionic Liquids

40.5 Conclusion and Outlook

References

Part VI: Bioorganometallic Chemistry

Chapter 41: Metal Carbonyls for CO-Based Therapies: Challenges and Successes

41.1 Introduction

41.2 CO in Biology and in Therapy—Origin, Targets, and Therapeutic Potential

41.3 Therapeutic Delivery of CO

41.4 Final Remarks and Perspectives

References

Chapter 42: The Ferrocifen Family as Potent and Selective Antitumor Compounds: Mechanisms of Action

42.1 Introduction

42.2 Context and Background

42.3 Ferrocene and Medicinal Chemistry

42.4 Synthesis and Behavior of Ferrocifen Derivatives

42.5 Synthesis and Behavior of Ferrocenophane Derivatives

42.7 Formulation: Research into Nanocapsules Best Suited for In Vivo Testing of Ferrocifens

42.8 Conclusion

Acknowledgements

References

Chapter 43: On The Track to Cancer Therapy: Paving New Ways with Ruthenium Organometallics

43.1 Introduction

43.2 Our Strategy in Bioorganometallic Chemistry

43.3 Biological Activity

43.4 Distribution in the Blood

43.5 Intracellular Distribution

43.6 Mechanisms of Action

43.7 Final Remarks

Acknowledgments

References

Chapter 44: Organometallic Chemistry of Rhenium and Technetium Fueled by Biomedical Applications

44.1 Introduction

44.2 Basic Concepts on Nuclear Medicine and Radiopharmaceuticals

44.3 Re(I) and Tc(I) Tricarbonyl Precursors

44.4 Organometallic Building Blocks for the Design of Radiopharmaceuticals

44.5 Perfusion Agents

44.6 Target-Specific Complexes

44.7 Concluding Remarks

References

Chapter 45: Metal-Based Indolobenzazepines and Indoloquinolines: from Moderate cdk Inhibitors to Potential Antitumor Drugs

45.1 Introduction

45.2 Indolobenzazepines as Moderate cdk Inhibitors

45.3 Toward Metal-Based Indolobenzazepines as Potential Anticancer Drugs

45.4 Indolo[3,2-c]Quinolines and their Metal Complexes

45.5 Outlook

Acknowledgments

References

Chapter 46: Metal-Based Chelates and Nanosystems as MRI Contrast Agents

46.1 Introduction

46.2 Magnetic Resonance Imaging

46.3 Contrast Enhancement

46.4 Contrast Agents

46.5 T1 Contrast Agents

46.6 T2 Contrast Agents

46.7 Classification of Contrast Agents

46.8 Nanocarriers

References

Part VII: Organometallic Electrochemistry

Chapter 47: Electrochemistry and Supramolecular Interactions of “Ferrocifen” Anticancer Drugs with Cyclodextrins and Lipid Bilayers: An Electrochemical Overview

47.1 Introduction

47.2 Deciphering the Activation Sequence of Ferrocifens

47.3 Supramolecular Interactions of Ferrocifens With Cyclodextrins and Lipid Bilayers

47.4 Conclusion

Acknowledgments

References

Chapter 48: Electrochemistry of Fischer Aminocarbene Complexes: Effects of Structure on Redox Properties, Electron Distribution, and Reaction Mechanisms

48.1 Introduction

48.2 Value of Electrochemistry

48.3 Fundamental Electrochemical Behavior of Aminocarbene Complexes

48.4 Basic Group of Aminocarbenes

48.5 Hetaryl Chromium(0) Aminocarbenes

48.6 Mechanistic Investigations

48.7 Comparison of Aminocarbene and Alkoxycarbene Complexes

48.8 Summary

References

Chapter 49: Electron Transfer-Induced Coordination Changes in Organometallic Complexes with Noninnocent Hemilabile Ligands

49.1 Introduction

49.2 Discussion of Results

49.3 Concluding Remarks

Acknowledgments

References

Chapter 50: Redox Potential–Structure Relationships and Parameterization in Characterization and Identification of Organometallic Compounds

50.1 Introduction

50.2 Parameterization of Ligands and Metal Centers

50.3 Final Comments

Acknowledgments

Abbreviations

References

Chapter 51: Endohedral Metallofullerenes Today: More and More Versatile Ships in Multiform Bottles—Electrochemistry of X-Ray Characterized Monometallofullerenes

51.1 Introduction

51.2 C60-Monometal Endohedral Metallofullerenes

51.3 C72-Monometal Endohedral Metallofullerenes

51.4 C74-Monometal Endohedral Metallofullerenes

51.5 C80-Monometal Endohedral Metallofullerenes

51.6 C82-Monometal Endohedral Metallofullerenes

51.7 C84-Monometal Endohedral Metallofullerenes

51.8 C90-Monometal Endohedral Metallofullerenes

51.9 C92-Monometal Endohedral Metallofullerenes

51.10 C94-Monometal Endohedral Metallofullerenes

51.11 Conclusion

51.12 Aknowledgment

References

Postscript: A Short History of the ICOMC Conferences

1 Introduction

2 Historical Development of the ICOMC Conferences

Acknowledgments

Index

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Library of Congress Cataloging-in-Publication Data:

Advances in organometallic chemistry and Catalysis : the silver/gold jubilee International Conference on

Organometallic Chemistry celebratory book / edited by Armando J. L. Pombeiro.

pages cm

“A John Wiley & Sons, Inc. publication.”

“Published simultaneously in Canada”–Title page verso.

Includes bibliographical references and index.

ISBN 978-1-118-51014-8 (cloth)

1. Organometallic chemistry–Research–Congresses. 2. International Conference on Organometallic

Chemistry–Anniversaries, etc. I. Pombeiro, A. J. L. (Armando J. L.) II. International Conference on

Organometallic Chemistry.

QD410.A39 2013

547′.05–dc23

2013026531

Preface

1.1 Organometallic Chemistry, The Science And Applications

Organometallic chemistry concerns the compounds with carbon–metal bonds, but, in a broader sense, deals with (i) transformations of organic compounds with the assistance of metals or (ii) even organometallic-type compounds that bear a metalloid or a nonmetal instead of a metal. This wide meaning is followed in this book.

Although Prussian blue, nowadays known to concern cyano-iron complexes, is present in colored pigments that had already been used in the antiquity, the first organometallic synthesis appears to have been achieved (in 1760) at a military pharmacy in Paris by Cadet, who, when studying inks based on cobalt salts (containing As), obtained a malodorous fuming liquid containing cacodyl oxide [(Me2As)2O] and tetramethyldiarsine, compounds of organo-arsenium that were identified only later. However, the Zeise's salt Na[PtCl3(η2-C2H4)], a π-complex of ethylene and Pt, prepared in 1827, is usually considered to be the first organometallic compound to be reported. The chemistry of the metal–carbon bond compounds has developed in a systematic manner since the middle of the nineteenth century, with works, for example, by Bunsen (who prepared and tasted (!) [Me2AsCN], in 1840) and his disciple Frankland (since 1849) who appears to have introduced the term “organometallic.” During the same century, a diversity of organometallic compounds were prepared by him and/or others (namely, Löwig, Schweizer, Hallwachs, Schafarik, Friedel, Crafts, Wanklyn, Schützenberger, Mond, and Berthelot), including organo-Zn, organo-Hg, organo-B, organo-Pb, organo-Al, organo-Si compounds and the first metal-carbonyls. The end of that century and beginning of the next one (the twentieth century) witnessed the development of organomagnesium compounds (by Barbier and his disciple Grignard) and the emergence of catalysis, in which organometallic chemistry played a fundamental role (e.g., Sabatier, Fischer, Tropsch, Roelen).

The growth of organometallic chemistry during the twentieth century was impressive (it is not possible in this short preface even to list the main achievements) and it became one of the fields of chemistry that has expanded mostly in the past decades, as attested, for example, by the good number of relevant international journals, huge number of papers, and prominent international conferences dealing with it, as well as by the many Nobel prizes awarded to scientists on account of their contributions within that overall field, namely, Grignard and Sabatier (1912); Ziegler and Natta (1963); Crowfoot-Hodgkin (1964); Fisher and Wilkinson (1973); Lipscomb (1976); Brown and Wittig (1979); Hoffmann and Fukui (1981); Taube (1983); Knowles, Noyori, and Sharpless (2001); Chauvin, Grubbs, and Schrock (2005); Heck, Negishi, and Suzuki (2010) (adding up already to nine prize winners in the current century!).

The influence of organometallic chemistry on the development of other fields of chemistry and other sciences has been growing in such an interdisciplinary way that nowadays organometallic chemistry interfaces with most of branches of chemistry and also with materials science, biology, pharmacology, etc.; so, naturally it should be viewed in a much broader sense than the strict requirement of M–C bonds, as mentioned above.

Catalysis conceivably provides the current highest contribution of chemistry toward sustainable development, and organometallic catalysis, in particular, promotes the use of carbon compounds and feedstocks for synthetic applications under milder conditions (energy saving) and superior selectivities (waste reduction), with resulting cost savings.

Development of systems operating under environmentally benign conditions toward the establishment of sustainable energy processes (e.g., artificial photosynthesis for conversion of carbon dioxide, dye-sensitized solar cells) is a scientific challenge that has been pursued by organometallic chemistry and catalysis.

Therefore, Organometallic Chemistry and Catalysis have grown in synergy and often indissoluble links can be disclosed. Organometallic compounds, under different perspectives, are involved in very important applications, such as

Activation

of small molecules with industrial, environmental, biological, or pharmacological significance, for example, alkanes (including natural gas and oil), olefins, carbon monoxide and carbon dioxide, and dihydrogen.

Hence, the petrochemical industry and carbon dioxide fixation (e.g., to prevent global warming) illustrate relevant fields of application of organometallic chemistry.

Synthesis

of important added value organic compounds, in both

commodity and fine chemistries

(large- and low-scale productions, respectively), namely, via catalytic processes where reactions are accelerated by organometallic catalysts. Examples of the former are polymers, carboxylic acids, aldehydes, alcohols, and ketones. Examples of the latter are compounds with biological/pharmacological activity.

New carbon materials

with a diversity of potential applications.

Apart from being widely used in industry, organometallic chemistry is also connected to biology, as there are enzymes that present organometallic active centers and catalyze organometallic reactions, which constitute inspiring biological motifs for development. Accordingly, bioorganometallic chemistry is a promising field with pharmacological and biomedical applications.

1.2 This Book and The International Conferences on Organometallic Chemistry (ICOMC)

An important indicator of the strength and health of organometallic chemistry is the organization of a large number of important international conferences dealing with this science, the most representative ones being the prestigious series of International Conferences on Organometallic Chemistry (ICOMC), which was launched in 1963 when the first conference was held in Cincinnati. This book follows the XXV ICOMC, which was held in Lisbon (2012) and gathered over 1200 delegates (circa 1100 being foreigners) from 54 countries, in spite of the world economic crisis and the competition with other relevant congresses in chemistry in the same year. It intends to celebrate the Silver edition (twenty-fifth edition) and the Gold year (fiftieth year since the first conference) of the series, constituting the major Silver/Gold Jubilee celebratory initiative of the ICOMCs.

The coinage of a medal (Fig. 1) on the occasion of the XXV ICOMC was another celebratory initiative, honoring the places where all these conferences have been held, and relevant landmarks in the history of this science: the ferrocene molecule (the conference logo) and the Chatt–Dewar–Duncanson model of ethylene coordination.

Figure 1.1 ICOMC Silver/Gold Jubilee medal.

Further details on the XXV ICOMC, including the distributions of participants from countries and particulars of their contributions by scientific areas, as well as a review on representative works presented therein and concerning the platinum group metals are found in [1].

Although the invited authors of this book have been Speakers at the XXV ICOMC, the book is neither the Proceedings of the Conference nor a conventional book with comprehensive and long chapters, but instead is aimed (i) to present recent advances and hot topics of current interest (with the concepts behind them, illustrative relevant cases, and their prospects) , (ii) to highlight the synergy between Organometallic Chemistry and Catalysis, and (iii) to show the versatility, richness, and potential of Organometallic Chemistry (in the broad sense) and Catalysis, including their relations with other sciences, that is, their boosting interdisciplinarity.

It provides an updated account of the scientific and applied interest and prospect of major fields of chemistry with high relevance in modern perspectives of science.

It can also be an inspiration for research topics for PhD and MSc theses, projects, and research lines. It is addressed to both expert and nonexpert readers, allowing the latter to get the sensitivity and encouragement for the field.

The main topics of the book follow the general areas of the XXV ICOMC itself. Catalysis was the most represented area (circa 22% of the total contributions), followed by Fundamental Organometallic Chemistry (circa 13%). Other areas (which, nevertheless can include the ones already mentioned or significantly overlap with them) can be ordered as follows: Activation of Small Molecules, C–H and C–C Bond Activation and Functionalization, Metal-Mediated Synthesis (each with circa 7%); Organometallic and Green Chemistry, Bioorganometallic and Bioinorganic Chemistry, Organometallics-Related Chemistry (each with circa 6%); Organometallics for Materials (circa 5%); Polynuclear and Supramolecular Assemblies, Polymers, and Reaction Mechanisms (circa 4% each); Theoretical and Physical Methods, Electrochemistry, and others.

These areas are assembled in the following main sections of the Book:

Activation and Functionalization of Carbon Single Bonds and of Small Molecules;

Organometallic Synthesis and Catalysis;

Organometallic Polymerization Catalysis;

Organometallic Polymers and Materials;

Organometallic Chemistry and Sustainable Energy;

Bioorganometallic Chemistry;

Organometallic Electrochemistry.

Catalysis is the driving force within most of these sections (areas), thus being the most represented overall area of the book, also in accord with what turned out to be the main interest of the conference attendees, reflecting the current organometallic scientific community in general. However, the other areas are not neglected and some of them, with particularly promising prospects, are even emphasized herein relative to their quota at the conference.

The book ends with a postscript providing a brief historical summary of the ICOMCs.

As a recognition of the innovative character of Organometallic Chemistry and Catalysis, providing novel routes to the discoveries of science, the cover picture of this book is inspired on the Monument of the Discoveries, at the mouth of the river Tejo (Tagus), Belém, Lisboa, which, with its rising boat prow shape, celebrates the (Portuguese) discoveries of new lands and sea routes during the fifteenth and sixteenth centuries.

As editor of this book and Chairman of the XXV ICOMC, I acknowledge the authors of the various chapters for their valuable contributions (an asterisk has been assigned to the correspondence authors' names who have requested so), and the members of the International Advisory Board (IAB) of the ICOMC for having accepted my proposals for this and the other celebratory initiatives. The support of the Portuguese Electrochemical Society is also acknowledged. Special thanks are due to Dr. Fatima Guedes da Silva and Dr. Manas Sutradhar for their inestimable and generous editorial assistance. The support of the Portuguese Electrochemical Society is also acknowledged.

Armando J. L. Pombeiro

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Lisboa, Portugal

Reference

1. Guedes da Silva, M. F. C.; Pombeiro, A. J. L. XXV International Conference on Organometallic Chemistry. Vital role of platinum group metals at Jubilee conference. Platinum Metals Rev. 2013, 57, 17–31, DOI: http://dx.doi.org/10.1595/147106713X659127.

Contributors

Pedro Adão, Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Lisboa, Portugal

Christian Amatore, Département de Chimie, Ecole Normale Supérieure, Paris, France

Toru Amaya, Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Osaka, Japan

Vânia André, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Lisboa, Portugal

Nibret G. Akalework, Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan, Republic of China

Luis G. Alves, Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Lisboa, Portugal

Michele Aresta, Department of Chemistry, University of Bari, Bari, Italy

Vladimir B. Arion, Institute of Inorganic Chemistry, University of Vienna, Vienna, Austria

Delele Worku Ayele, Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan, Republic of China

Fabrizia Fabrizi de Biani, Dipartimento di Chimica dell'Università di Siena, Siena, Italy

Shanmuga Bharathi, Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Lisboa, Portugal

Natalia Belkova, A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences, Moscow, Russia

Vadim Boyarskiy, Department of Chemistry, St. Petersburg State University, St. Petersburg, Russia

Pierre Braunstein, Laboratoire de Chimie de Coordination, Institut de Chimie, Université de Strasbourg, Strasbourg, France