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.

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

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.