ADVANCES IN ORGANOMETALLIC CHEMISTRY AND CATALYSIS ADVANCES IN ORGANOMETALLIC CHEMISTRY AND CATALYSIS The Silver/Gold Jubilee International Conference on Organometallic Chemistry Celebratory Book Edited by ARMANDO J. L. 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QD410.A392013 547(cid:2).05–dc23 2013026531 PrintedintheUnitedStatesofAmerica 10987654321 CONTENTS 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 GeorgiyB.Shul’pin 2 Toward Functionalization of Alkanes Under Environmentally Benign Conditions 15 ArmandoJ.L.Pombeiro 3 Self-assembled Multicopper Complexes and Coordination Polymers for Oxidation and Hydrocarboxylation of Alkanes 27 AlexanderM.Kirillov,MarinaV.Kirillova,andArmandoJ.L.Pombeiro 4 Activation of C—O and C—F Bonds by Pincer-iridium Complexes 39 JasonHackenberg,KarstenKrogh-Jespersen,andAlanS.Goldman 5 Functionalization of sp2 and sp3 Carbon Centers Catalysed by Polyoxometalates and Metalloporphyrins 59 Ma´rioM.Q.Simo˜es,IsabelC.M.S.Santos,MariaGrac¸aP.M.S.Neves,AnaM.V.Cavaleiro,andJose´ 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,andI.A.Godovikov 7 Transition-metal-promoted Functionalization of Carboranes 81 ZaozaoQiuandZuoweiXie 8 Weak Interactions and M—H Bond Activation 97 ElenaShubina,NataliaBelkova,OlegFilippov,andLinaEpstein v vi CONTENTS PART II ORGANOMETALLIC SYNTHESIS AND CATALYSIS 111 9 Complexes with Protic N-Heterocyclic Carbene (NR,NH-NHC) Ligands 113 F.EkkehardtHahn 10 Cyclopentadienyl-functionalized N-Heterocyclic Carbene Complexes of Iron and Nickel: Catalysts for Reductions 133 BeatrizRoyo 11 Palladium-(acyclic diaminocarbene) Species as Alternative to Palladium-(nitrogen heterocyclic carbenes) in Cross-coupling Catalysis 145 VadimP.Boyarskiy,KonstantinV.Luzyanin,andVadimYu.Kukushkin 12 Synthesis of Metallocenes Via Metathesis in Metal Coordination Spheres 157 AntoniPietrzykowskiandWłodzimierzBuchowicz 13 Metal-mediated [2 + 3] Dipolar Cycloaddition to Substrates with CN Triple Bond: Recent Advances 171 KonstantinV.LuzyaninandMaximL.Kznetsov 14 Coordination Chemistry of Oxazoline/Thiazoline-based P,N Ligands 185 ShuanmingZhang,RobertoPattacini,andPierreBraunstein 15 “Click” Copper Catalyzed Azide-alkyne Cycloaddition (CuAAC) in Aqueous Medium 199 Joaqu´ınGarc´ıa-A´lvarezandJose´ Gimeno 16 Organogold Catalysis: Homogeneous Gold-catalyzed Transformations for a Golden Jubilee 207 FabienGagosz 17 Vanadium(IV) Complexes Derived from Aromatic o-Hydroxyaldehydes and Tyrosine Derivatives: Catalytic Evaluation in Sulfoxidations 227 Joa˜oCostaPessoa,IsabelCorreia,andPedroAda˜o 18 Microwave-assisted Catalytic Oxidation of Alcohols to Carbonyl Compounds 233 YauhenYu.Karabach,MaximilianN.Kopylovich,KamranT.Mahmudov,andArmandoJ.L.Pombeiro 19 Oxidation of Glycerol with Hydrogen Peroxide Catalyzed by Metal Complexes 247 DalmoMandelli,WagnerA.Carvalho,LidiaS.Shul’pina,AlexanderM.Kirillov,MarinaV.Kirillova, ArmandoJ.L.Pombeiro,andGeorgiyB.Shul’pin 20 Involvement of an Acetato Ligand in the Reductive Elimination Step of the Rhodium-catalyzed Methanol Carbonylation 259 DucHanhNguyen,NicolasLassauque,ThomasDavin,LaurentMaron,CaroleLeBerre,PhilippeSerp, andPhilippeKalck 21 Half-sandwich Rhodium(III), Iridium(III), and Ruthenium(II) Complexes with Ancillary Pyrazole-based Ligands 269 ClaudioPettinari,RiccardoPettinari,CorradoDiNicola,andFabioMarchetti 22 Carbon-scorpionate Complexes in Oxidation Catalysis 285 Lu´ısaM.D.R.S.MartinsandArmandoJ.L.Pombeiro 23 Toward Chemoselective Bioconjugative Desulfitative Catalysis 295 LannyS.LiebeskindandEthelC.Garnier-Amblard CONTENTS vii 24 Sulfoxide Redox Chemistry with Molybdenum Catalysts 305 MariaJose´ CalhordaandLuisF.Veiros 25 A New Family of Zirconium Complexes Anchored by Dianionic Cyclam-based Ligands: Syntheses, Structures, and Catalytic Applications 315 AnaM.Martins,RuiF.Munha´,LuisG.Alves,andShanmugaBharathi 26 Metal-organo Multicatalysis: An Emerging Concept 325 AlexandreF.Trindade,Joa˜oN.Rosa,Fa´bioM.F.Santos,andPedroM.P.Gois PARTIII 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 MarcVisseaux,ThomasChenal,andPhilippeZinck 28 Charge-neutral and Cationic Complexes of Large Alkaline Earths for Ring-opening Polymerization and Fine Chemicals Catalysis 359 Jean-Franc¸oisCarpentier,BoLiu,andYannSarazin PARTIV ORGANOMETALLIC POLYMERS AND MATERIALS 379 29 Organometallic Polymers 381 ManuelSerrano-Ruiz,FrancoScalambra,andAntonioRomerosa 30 From Serendipity to Porosity: Synthesis and Reactivity of Coordination Polymers Based on Copper Trinuclear Triangular Motifs 407 LucianoPandolfo 31 Organometallic Nanoparticles 421 PatriciaLara,KarinePhilippot,Lise-MarieLacroix,Se´bastienLachaize,NikosLiakakos,KaterinaSoulantica, andBrunoChaudret 32 Organometallic Compounds in the Synthesis of New Materials: Old Ligands, New Tricks 437 PiotrSobotaandŁukaszJohn 33 The Role of Organometallic Complexes in the Synthesis of Shaped Carbon Materials 445 NeilJ.CovilleandEdwardN.Nxumalo 34 Metal Catalysis in Fullerene Chemistry 459 SalvatoreFilippone,EnriqueE.Maroto,A´ngelMart´ın-Domenech,andNazarioMart´ın 35 Organometallic Complexes of Sumanene 473 ToruAmayaandToshikazuHirao 36 Advances in Luminescent Tetracoordinate Organoboron Compounds 485 D.SureshandPedroT.Gomes 37 Mechanochemistry: A Tool in the Synthesis of Catalysts, Metallodrugs, and Metallopharmaceuticals 493 VaˆniaAndre´,ClaraS.B.Gomes,andM.TeresaDuarte viii CONTENTS PART V ORGANOMETALLIC CHEMISTRY AND SUSTAINABLE ENERGY 501 38 Organometallic Complexes for Dye-sensitized Solar Cells (DSSC) 503 DeleleW.Ayele,Wei-NeinSu,JohnRick,Hung-MingChen,Chun-JernPan,NibretG.Akalework, andBing-JoeHwang 39 Synthetic Photosynthesis for the Conversion of Large Volumes of Carbon Dioxide into Energy-Rich Molecules: Saving Fossil Fuels by Recycling Carbon 513 MicheleArestaandAngelaDibenedetto 40 Ionic Liquids for Hydrogen Storage: Opportunities for Organometallic Chemistry 529 MartinH.G.PrechtlandSebastianSahler PARTVI BIOORGANOMETALLIC CHEMISTRY 543 41 Metal Carbonyls for CO-based Therapies: Challenges and Successes 545 CarlosC.Roma˜oandHelenaL.A.Vieira 42 The Ferrocifen Family as Potent and Selective Antitumor Compounds: Mechanisms of Action 563 Ge´rardJaouenandSidenTop 43 On the Track to Cancer Therapy: Paving New Ways With Ruthenium Organometallics 581 TaˆniaS.MoraisandM.HelenaGarcia 44 Organometallic Chemistry of Rhenium and Technetium Fueled by Biomedical Applications 589 Anto´nioPaulo,GoretiRibeiroMorais,andIsabelSantos 45 Metal-based Indolobenzazepines and Indoloquinolines: From Moderate cdk Inhibitors to Potential Antitumor Drugs 605 MichaelF.Primik,LukasK.Filak,andVladimirB.Arion 46 Metal-based Chelates and Nanosystems as MRI Contrast Agents 619 SaraFigueiredoandCarlosF.G.C.Geraldes PARTVII ORGANOMETALLIC ELECTROCHEMISTRY 631 47 Electrochemistry and Supramolecular Interactions of “Ferrocifen” Anticancer Drugs with Cyclodextrins and Lipid Bilayers: An Electrochemical Overview 633 OlivierBuriez,EricLabbe´,andChristianAmatore 48 Electrochemistry of Fischer Aminocarbene Complexes: Effects of Structure on Redox Properties, Electron Distribution, and Reaction Mechanisms 653 Jirˇ´ıLudv´ıkandIrenaHoskovcova´ 49 Electron Transfer-induced Coordination Changes in Organometallic Complexes with Non-innocent Hemilabile Ligands 667 WolfgangKaim,MartinaBubrin,andRalphHu¨bner 50 Redox Potential–Structure Relationships and Parameterization in Characterization and Identification of Organometallic Compounds 677 M.Fa´timaC.GuedesdaSilvaandArmandoJ.L.Pombeiro