Advances in Organometallic Chemistry and Catalysis The Silver / Gold Jubilee International Conference on Organometallic Chemistry Celebratory Book

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.

ARMANDO J. L. POMBEIRO is Full Professor at the Instituto Superior Técnico in Lisbon (Portugal), Full Member of the Academy of Sciences of Lisbon (in charge of various directive and representative positions) and President of the Portuguese Electro-chemical Society. His research group investigates the activation of small molecules with industrial, environmental or biological significance, including metal-mediated synthesis and catalysis (e.g., functionalization of alkanes under mild conditions), crystal engineering of coordination compounds, design and self-assembly of polynuclear and supramolecular structures, molecular electrochemistry and theoretical studies. He was Chairman of the 25th ICOMC and member of organizing/scientific committees of 40 international conferences or schools. He authored one book (plus three as editor), (co-)authored 600 research publications, 33 patents, and presented 90 invited lectures at international conferences. His work has received ca. 11,000 citations, h-index = 48 (ISI Web of Knowledge). Among his many honors, Dr. Pombeiro has been awarded the Madinabeitia-Lourenço Prize from the Spanish Royal Chemical Society.

PREFACE xi

CONTRIBUTORS xv

PART I ACTIVATION AND FUNCTIONALIZATION OF CARBON SINGLE BONDS AND OF SMALL
MOLECULES 1

1 Organometallic Complexes as Catalysts in Oxidation of C—H Compounds 3
Georgiy B. Shul’pin

2 Toward Functionalization of Alkanes Under Environmentally Benign Conditions 15
Armando J. L. Pombeiro

3 Self-assembled Multicopper Complexes and Coordination Polymers for Oxidation and Hydrocarboxylation of Alkanes 27
Alexander M. Kirillov, Marina V. Kirillova, and Armando J. L. Pombeiro

4 Activation of C—O and C—F Bonds by Pincer-iridium Complexes 39
Jason Hackenberg, Karsten Krogh-Jespersen, and Alan S. Goldman

5 Functionalization of sp2 and sp3 Carbon Centers Catalysed by Polyoxometalates and Metalloporphyrins 59
M´ario M. Q. Sim˜oes, Isabel C. M. S. Santos, Maria Gra¸ca P. M. S. Neves, Ana M. V. Cavaleiro, and Jos´e A. S. Cavaleiro

6 Quasi-borinium Cation Based on Cobalt Bis(dicarbollide): Its Lewis Acidity and C—H and C—X Bond Activation 73
V. I. Bregadze, I. B. Sivaev, I. D. Kosenko, I. A. Lobanova, Z. A. Starikova, and I. A. Godovikov

7 Transition-metal-promoted Functionalization of Carboranes 81
Zaozao Qiu and Zuowei Xie

8 Weak Interactions and M—H Bond Activation 97
Elena Shubina, Natalia Belkova, Oleg Filippov, and Lina Epstein

PART II ORGANOMETALLIC SYNTHESIS AND CATALYSIS 111

9 Complexes with Protic N-Heterocyclic Carbene (NR,NH-NHC) Ligands 113
F. Ekkehardt Hahn

10 Cyclopentadienyl-functionalized N-Heterocyclic Carbene Complexes of Iron and Nickel: Catalysts for Reductions 133
Beatriz Royo

11 Palladium-(acyclic diaminocarbene) Species as Alternative to Palladium-(nitrogen heterocyclic carbenes) in Cross-coupling Catalysis 145
Vadim P. Boyarskiy, Konstantin V. Luzyanin, and Vadim Yu. Kukushkin

12 Synthesis of Metallocenes Via Metathesis in Metal Coordination Spheres 157
Antoni Pietrzykowski and W??odzimierz Buchowicz

13 Metal-mediated [2 + 3] Dipolar Cycloaddition to Substrates with CN Triple Bond: Recent Advances 171
Konstantin V. Luzyanin and Maxim L. Kznetsov

14 Coordination Chemistry of Oxazoline/Thiazoline-based P,N Ligands 185
Shuanming Zhang, Roberto Pattacini, and Pierre Braunstein

15 “Click” Copper Catalyzed Azide-alkyne Cycloaddition (CuAAC) in Aqueous Medium 199
Joaqu´??n Garc´??a-A´lvarez and Jose´ Gimeno

16 Organogold Catalysis: Homogeneous Gold-catalyzed Transformations for a Golden Jubilee 207
Fabien Gagosz

17 Vanadium(IV) Complexes Derived from Aromatic o-Hydroxyaldehydes and Tyrosine Derivatives: Catalytic Evaluation in Sulfoxidations 227
Jo˜ao Costa Pessoa, Isabel Correia, and Pedro Ad˜ao

18 Microwave-assisted Catalytic Oxidation of Alcohols to Carbonyl Compounds 233
Yauhen Yu. Karabach, Maximilian N. Kopylovich, Kamran T. Mahmudov, and Armando J. L. Pombeiro

19 Oxidation of Glycerol with Hydrogen Peroxide Catalyzed by Metal Complexes 247
Dalmo Mandelli, Wagner A. Carvalho, Lidia S. Shul’pina, Alexander M. Kirillov, Marina V. Kirillova,
Armando J. L. Pombeiro, and Georgiy B. Shul’pin

20 Involvement of an Acetato Ligand in the Reductive Elimination Step of the Rhodium-catalyzed Methanol Carbonylation 259
Duc Hanh Nguyen, Nicolas Lassauque, Thomas Davin, Laurent Maron, Carole Le Berre, Philippe Serp, and Philippe Kalck

21 Half-sandwich Rhodium(III), Iridium(III), and Ruthenium(II) Complexes with Ancillary Pyrazole-based Ligands 269
Claudio Pettinari, Riccardo Pettinari, Corrado Di Nicola, and Fabio Marchetti

22 Carbon-scorpionate Complexes in Oxidation Catalysis 285
Lu´??sa M. D. R. S. Martins and Armando J. L. Pombeiro

23 Toward Chemoselective Bioconjugative Desulfitative Catalysis 295
Lanny S. Liebeskind and Ethel C. Garnier-Amblard

24 Sulfoxide Redox Chemistry with Molybdenum Catalysts 305
Maria Jos´e Calhorda and Luis F. Veiros

25 A New Family of Zirconium Complexes Anchored by Dianionic Cyclam-based Ligands: Syntheses,
Structures, and Catalytic Applications 315
Ana M. Martins, Rui F. Munh´a, Luis G. Alves, and Shanmuga Bharathi

26 Metal-organo Multicatalysis: An Emerging Concept 325
Alexandre F. Trindade, Jo˜ao N. Rosa, F´abio M. F. Santos, and Pedro M. P. Gois

PART III ORGANOMETALLIC POLYMERIZATION CATALYSIS 343

27 Coordinative Chain Transfer Polymerisations and Copolymerisations by Means of Rare Earths
Organometallic Catalysts for the Synthesis of Tailor-made Polymers 345
Marc Visseaux, Thomas Chenal, and Philippe Zinck

28 Charge-neutral and Cationic Complexes of Large Alkaline Earths for Ring-opening Polymerization
and Fine Chemicals Catalysis 359
Jean-Fran¸cois Carpentier, Bo Liu, and Yann Sarazin

PART IV ORGANOMETALLIC POLYMERS AND MATERIALS 379

29 Organometallic Polymers 381
Manuel Serrano-Ruiz, Franco Scalambra, and Antonio Romerosa

30 From Serendipity to Porosity: Synthesis and Reactivity of Coordination Polymers Based on Copper Trinuclear Triangular Motifs 407
Luciano Pandolfo

31 Organometallic Nanoparticles 421
Patricia Lara, Karine Philippot, Lise-Marie Lacroix, S´ebastien Lachaize, Nikos Liakakos, Katerina Soulantica, and Bruno Chaudret

32 Organometallic Compounds in the Synthesis of New Materials: Old Ligands, New Tricks 437
Piotr Sobota and ??ukasz John

33 The Role of Organometallic Complexes in the Synthesis of Shaped Carbon Materials 445
Neil J. Coville and Edward N. Nxumalo

34 Metal Catalysis in Fullerene Chemistry 459
Salvatore Filippone, Enrique E. Maroto, A´ngel Mart´??n-Domenech, and Nazario Mart´??n

35 Organometallic Complexes of Sumanene 473
Toru Amaya and Toshikazu Hirao

36 Advances in Luminescent Tetracoordinate Organoboron Compounds 485
D. Suresh and Pedro T. Gomes

37 Mechanochemistry: A Tool in the Synthesis of Catalysts, Metallodrugs, and Metallopharmaceuticals 493
Vˆania Andr´e, Clara S. B. Gomes, and M. Teresa Duarte

PART V ORGANOMETALLIC CHEMISTRY AND SUSTAINABLE ENERGY 501

38 Organometallic Complexes for Dye-sensitized Solar Cells (DSSC) 503
Delele W. Ayele, Wei-Nein Su, John Rick, Hung-Ming Chen, Chun-Jern Pan, Nibret G. Akalework, and Bing-Joe Hwang

39 Synthetic Photosynthesis for the Conversion of Large Volumes of Carbon Dioxide into Energy-Rich Molecules: Saving Fossil Fuels by Recycling Carbon 513
Michele Aresta and Angela Dibenedetto

40 Ionic Liquids for Hydrogen Storage: Opportunities for Organometallic Chemistry 529
Martin H. G. Prechtl and Sebastian Sahler

PART VI BIOORGANOMETALLIC CHEMISTRY 543

41 Metal Carbonyls for CO-based Therapies: Challenges and Successes 545
Carlos C. Rom˜ao and Helena L. A. Vieira

42 The Ferrocifen Family as Potent and Selective Antitumor Compounds: Mechanisms of Action 563
G´erard Jaouen and Siden Top

43 On the Track to Cancer Therapy: Paving New Ways With Ruthenium Organometallics 581
Tˆania S. Morais and M. Helena Garcia

44 Organometallic Chemistry of Rhenium and Technetium Fueled by Biomedical Applications 589
Ant´onio Paulo, Goreti Ribeiro Morais, and Isabel Santos

45 Metal-based Indolobenzazepines and Indoloquinolines: From Moderate cdk Inhibitors to Potential Antitumor Drugs 605
Michael F. Primik, Lukas K. Filak, and Vladimir B. Arion

46 Metal-based Chelates and Nanosystems as MRI Contrast Agents 619
Sara Figueiredo and Carlos F. G. C. Geraldes

PART VII ORGANOMETALLIC ELECTROCHEMISTRY 631

47 Electrochemistry and Supramolecular Interactions of “Ferrocifen” Anticancer Drugs with Cyclodextrins and Lipid Bilayers: An Electrochemical Overview 633
Olivier Buriez, Eric Labb´e, and Christian Amatore

48 Electrochemistry of Fischer Aminocarbene Complexes: Effects of Structure on Redox Properties, Electron Distribution, and Reaction Mechanisms 653
Ji??r´?? Ludv´??k and Irena Hoskovcov´a

49 Electron Transfer-induced Coordination Changes in Organometallic Complexes with Non-innocent Hemilabile Ligands 667
Wolfgang Kaim, Martina Bubrin, and Ralph H¨ubner

50 Redox Potential–Structure Relationships and Parameterization in Characterization and Identification of Organometallic Compounds 677
M. F´atima C. Guedes da Silva and Armando J. L. Pombeiro

51 Endohedral Metallofullerenes Today: More and More Versatile Ships in Multiform Bottles—Electrochemistry of X-Ray Characterized Monometallofullerenes 691
Fabrizia Fabrizi de Biani and Piero Zanello

POSTSCRIPT: A SHORT HISTORY OF THE ICOMC CONFERENCES 703
Ekkehardt Hahn

INDEX 707

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