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      Metallabenzenes

      An Expert View

      AvL. James Wright

      Inbunden, Engelska, 2017

      2 132 kr

      Beställningsvara. Skickas inom 5-8 vardagar. Fri frakt över 249 kr.

      Beskrivning

      The only comprehensive book covering of advances in metallabenzene chemistry—written by the leading experts in the fieldMetallabenzenes: An Expert View provides comprehensive coverage of all aspects of metallabenzene chemistry, including syntheses, reactions, physical properties, and theoretical treatments of metallabenzenes. Fused ring metallabenzenes, heterometallabenzenes, and metallabenzenes that are p-bound to other metal fragments are also discussed in depth.Although benzene itself was discovered in 1825, it wasn’t until 1982 that the first metallabenzene was isolated. Since then, interest in these compounds has built steadily, and metallabenzene chemistry is now a flourishing sub discipline in its own right. A diverse range of synthetic approaches to these compounds have been devised, and new developments and discoveries have appeared regularly over the past several decades. Yet, until now, no books devoted to this fascinating and important class of chemical compounds have been available to researchers and students. This bookfills that gap in the literature with a comprehensive review of recent advances in metallabenzene chemistry theory and applications. Featuring contributions by an international group of experts in the field, each chapter summarizes important recent research in and significant contributions to various aspects of metallabenzene chemistry. Provides academics, researchers and graduate students with a comprehensive review of advances in metallabenzene researchCovers fused-ring metallabenzenes—including metallanaphthalenes, metallabenzofurans, and metallabenzothiophenes—as well as p-bound heterometallabenzenes and metallabenzenesReviews the latest computational studies that have led to the theoretical understanding of metallabenzenesIncludes critical discussions of metallabenzene aromaticity, an area rarely covered by computational expertsMetallabenzenes: An Expert View is an important working resource for those working in organometallic chemistry, aromaticity, coordination chemistry, theoretical chemistry, catalysis and materials science. It is also an excellent text for graduate-level courses in those areas.

      Produktinformation

      • Utgivningsdatum:2017-10-06
      • Mått:173 x 246 x 23 mm
      • Vikt:703 g
      • Format:Inbunden
      • Språk:Engelska
      • Antal sidor:352
      • Förlag:John Wiley & Sons Inc
      • ISBN:9781119068068

      Utforska kategorier

      • Organisk kemi inom Naturvetenskap och teknik

      Mer om författaren

      L. James Wright is a Professor in the School of Chemical Sciences, University of Auckland, New Zealand. Professor Wright has been an active researcher in the area of metallabenzenes for over 15 years and has published reviews and articles on various aspects of metallabenzene chemistry. His current research focuses on organometallic chemistry, including metallabenzenes and new carbon donor ligands, carbon donor ligands, development of new nitrogen donor ligands, macrocyclic complexes, CORMs, catalysis, oxidation chemistry and green chemistry.

      Innehållsförteckning

      • List of Contributors xiPreface xiii1 Metallabenzenes and Fused-Ring Metallabenzenes of Osmium, Ruthenium and Iridium: Syntheses, Properties and Reactions 1Benjamin J. Frogley, Warren R. Roper and L. James Wright1.1 Introduction 11.2 Syntheses and Properties of Metallabenzenes with Methylthiolate Substituents 21.2.1 Osmabenzenes 21.2.2 Iridabenzenes 71.3 Syntheses and Properties of Fused-Ring Metallabenzenes 101.3.1 Osmabenzofurans 111.3.2 Ruthenabenzofurans 141.3.3 Iridabenzofurans 171.3.4 Iridabenzothiophenes 191.3.5 Iridabenzothiazolium Cations 211.4 Reactions of Metallabenzenes and Metallabenzenoids 241.4.1 Electrophilic Aromatic Substitution Reactions 241.4.2 Rearrangement to Cyclopentadienyl Complexes 341.4.3 Nucleophilic Aromatic Substitution Reactions 381.5 Concluding Remarks 43References 432 The First Iridabenzenes: Syntheses, Properties, and Reactions 51John R. Bleeke2.1 Introduction 512.2 Basic Theory 522.3 Discovery of the First Stable Metallabenzenes 542.4 Synthesis of Iridabenzene 542.5 Valence Bond Structures and Electron Counting for Iridabenzene 562.6 The Tris(trimethylphosphine) Reaction System 572.7 Structure and Spectroscopy of Iridabenzene 3 582.8 Chemical Reactivity of Iridabenzene 3 602.8.1 Ligand Substitution 602.8.2 Oxidative Addition/Oxidation 632.8.3 Cycloaddition 652.8.4 Theoretical Study of Cycloaddition 682.8.5 Electrophilic Addition 692.8.6 Coordination to Mo(CO)3 712.9 Iridaphenol 732.10 Synthesis and Spectroscopy of Iridapyrylium 782.11 Valence Bond Structures and Electron Counting for Iridapyrylium 802.12 Chemical Reactivity of Iridapyrylium 37 802.12.1 Ligand Addition 802.12.2 Cycloaddition 812.13 Comparison of Iridabenzene 3 and Iridapyrylium 37 832.14 Synthesis and Spectroscopy of Iridathiabenzene 832.15 Structure of Iridathiabenzene 50 852.16 Chemical Reactivity of Iridathiabenzene 50 862.16.1 Ligand Addition and Cycloaddition 862.16.2 Coordination to Other Metals 862.17 Comparison of Iridathiabenzene 50 and Iridapyrylium 37 892.18 Synthesis and Structure of a Neutral Iridathiabenzene 892.19 Spectroscopy of Neutral Iridathiabenzene 56 902.20 Chemical Reactivity of Neutral Iridathiabenzene 56 912.21 Related Metal-Coordinated Metallabenzenes 942.22 Aromaticity 992.22.1 Electronic Structure 992.22.2 Structural (Geometric) Features 992.22.3 Magnetic Properties 1002.22.4 Stability 1002.22.5 Chemical Reactivity 1012.22.6 Conclusion 1012.23 Final Word 102References1023 Metallabenzenes and Valence Isomers via the Nucleophilic 3-Vinylcyclopropene Route 109Michael M. Haley3.1 Project Origin and Inspiration (A Nod to Binger, Bleeke, Grubbs, Hughes, and Roper) 1093.2 Ligand Synthesis (An Exercise in Over-Engineering) 1113.3 Iridabenzenes and Valence Isomers (Success after Six Long Years) 1143.3.1 Iridabenzene/Iridabenzvalene Synthesis 1143.3.2 Mechanisms of Iridabenzvalene Isomerization and Iridabenzene Rearrangement 1203.3.3 Iridabenzene/Iridabenzvalene Spectroscopic Properties 1233.3.4 Iridabenzene/Iridabenzvalene Solid]State Structures 1253.4 Platinabenzenes (How You Get Your Chemistry on a Beer Coaster) 1263.4.1 “Irrational” Platinabenzene Synthesis 1263.4.2 “Rational” Platinabenzene Synthesis 1293.4.3 Platinabenzene Spectroscopic Properties and Solid]State Structures 1303.5 Odds and Sods (Ones that Got Away) 1323.5.1 16]Electron, High Oxidation State Iridabenzenes 1333.5.2 Hammett Plot of Iridabenzvalene Isomerization 1353.5.3 Rhodabenzvalene and Putative Dewar Rhodabenzene 1373.6 Conclusion (So Long, and Thanks for All the Fish) 1393.7 Acknowledgements 140References 1404 Iridabenzenes and Iridanaphthalenes with Supporting Tris(pyrazolyl)borate Ligands 145Margarita Paneque and Nuria Rendón4.1 Introduction 1454.2 Synthetic Routes to Iridaaromatic Derivatives with Supporting Tris(pyrazolyl)borate Ligands 1464.2.1 Oxidatively Induced Ring Contraction 1464.2.2 Synthesis of Iridaaromatics by Ring Expansion Reactions 1484.2.2.1 Protonation of a Vinylidene]Iridacyclopentene 1494.2.2.2 Preparation of TpMe2]Iridaaromatics by Reaction of Olefins with Iridacyclopentadienes 1534.2.2.2.1 Iridabenzenes 1534.2.2.2.2 Iridanaphthalenes 1574.2.2.3 Other Procedures for Ring Expansion Reactions 1614.2.2.3.1 Reaction of a TpMe2-Iridaindene with Bis(trimethylsilyl)acetylene 1614.2.2.3.2 Coupling of Two Molecules of Acetylene and a Further C1 Fragment in a TpIr Precursor 1644.3 Reactivity of Iridaaromatics with Supporting Tris(pyrazolyl)borate ligands 1664.4 Structural Data for Iridaaromatics with Supporting Tris(pyrazolyl)borate Ligands 1714.5 Spectroscopic Data for Iridaaromatics with Supporting Tris(Pyrazolyl)Borate Ligands 1754.6 Conclusions 177References 1785 Chemistry of Metallabenzynes and Rhenabenzenes 185Guochen Jia5.1 Introduction 1855.2 Chemistry of Metallabenzynes 1865.2.1 Routes to Construct Metallabenzyne Rings 1865.2.1.1 Reactions of Terminal Alkynes with OsCl2(PPh3)3 1865.2.1.2 Reactions of Allenylcarbene and Vinylidene Complexes with Acetylides or Alkynes 1865.2.1.3 Oxidative Addition Reactions of Vinyl Carbyne Complexes 1885.2.1.4 Isomerization of Alkyne]Carbene Complexes 1895.2.2 Chemical Properties of Metallabenzynes 1895.2.2.1 Reactions Not Involving Carbons of the Metallabenzyne Ring 1895.2.2.2 Electrophilic Substitution Reactions 1915.2.2.3 Nucleophilic Addition Reactions 1935.2.2.4 Migratory Insertion Reactions 1935.2.3 Structural Properties of Metallabenzynes 2025.2.4 Ring Strain of Metallabenzynes 2035.2.5 Electronic Structures of Metallabenzynes 2045.2.5.1 Aromatic Properties of Metallabenzynes 2055.3 Chemistry of Rhenabenzenes 2075.3.1 Synthesis of Rhenabenzenes 2075.3.2 Structural and Aromatic Properties of Rhenabenzenes 2085.3.3 Rearrangement of Low]valent Rhenabenzene to η5]Cyclopentadienyl Complexes 2095.4 Summary 215References 2166 Metallabenzenoid Compounds Bearing Phosphonium Substituents 219Hong Zhang and Haiping Xia6.1 Synthesis 2206.1.1 [5+1] Synthesis 2206.1.1.1 Syntheses Starting from HC≡CCH(OH)C≡CH 2206.1.1.2 Syntheses Starting from HC≡CCH(OH)CH=CH2 and HC≡CCCH3(OH)CH=CH2 2236.1.1.3 Syntheses Starting from HC≡CCH(OH)Ph 2236.1.1.4 Synthesis Starting from HC≡CCH(OH)Et 2256.1.2 [4+2] Synthesis 2266.1.3 [3+3] Synthesis 2286.2 Structure and Bonding 2296.3 Reactions 2326.3.1 Ligand Substitution Reactions 2326.3.2 Nucleophilic Addition and Nucleophilic Aromatic Substitution Reactions 2336.3.3 Cycloaddition Reactions 2396.3.4 Formation of Unsaturated Organic Rings 2406.4 Physical Properties 2436.4.1 Electrochemical Properties 2446.4.2 Optical Properties 2476.4.3 Other Properties 2496.5 Polycyclic Metallabenzenoid Compounds Bearing Phosphonium Substituents 2496.5.1 Synthesis by Means of SNAr Reactions 2516.5.2 Synthesis by Means of Electrophilic Cyclization Reactions 2556.6 Future Prospects 261References 2627 Theoretical Studies of Metallabenzenes: From Bonding Situation to Reactivity 267Israel Fernández and Gernot Frenking7.1 Introduction 2677.2 Structure and Bonding Situation 2687.2.1 Bonding Situation and Molecular Orbitals 2687.2.2 Aromaticity of Metallabenzenes 2727.2.2.1 [4n+2]]rule 2737.2.2.2 Absolute Hardness 2737.2.2.3 Magnetic Descriptors 2747.2.2.4 Energetic Descriptors 2777.3 Computational Studies on Synthetic Pathways towards Metallabenzenes 2797.4 Computational Studies on the Reactivity of Metallabenzenes 2867.4.1 Electrophilic Aromatic Substitution Reactions 2867.4.2 Nucleophilic Aromatic Substitution Reactions 2887.4.3 Addition and Cycloaddition Reactions 2927.4.4 Rearrangement Reactions 2947.5 Concluding Remarks and Outlook 2967.6 Acknowledgements 297References 298Index 305
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