Note: Front cover -- Advances in Organometallic Chemistry -- Copyright page -- Contents -- Contributors -- Preface -- Chapter 1. A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation (Hydrosilylation) -- I. Introduction -- II. Hydrosilation with Iron Triad Catalysts -- III. Cobalt Triad Catalysts -- IV. Nickel-Triad Catalysts -- V. Group IVB, Group IIIB, Lanthanides and Actinides -- VI. Manganese, Rhenium and Copper -- VII. Catalysis by Acids, Bases, or Free Radicals -- VIII. Asymmetric Hydrosilation -- IX. Applied Aspects - Synthesis of Polymers and Materials -- X. Mechanistic Studies -- XI. Challenges and the Future of Hydrosilation -- Acknowledgments -- References -- Chapter 2. Organotransition Metal Complexes for Nonlinear Optics -- I. Introduction -- II. Theory and Techniques -- III. Molecular Second-Order Measurements -- IV. Molecular Third-Order Measurements -- V. Concluding Remarks -- Acknowledgment -- Appendix: Abbreviations -- References -- Chapter 3. Pentadienyl Complexes of the Group 4 Transition Metals -- I. Introduction -- II. Bis(η5-pentadienyl)Metal Complexes -- III. Mono(η5-pentadienyl)Metal Complexes -- IV. Miscellaneous Complexes -- V. Reaction Chemistry -- VI. Future Prospects -- Acknowledgment -- References -- Chapter 4. Mixed Metal Acetylide Complexes -- I. Introduction -- II. Mixed Group 8 Metal Acetylide Complexes -- III. Mixed Group 10 Metal Acetylide Complexes -- IV. Mixed Group 11 Metal Acetylide Complexes -- V. Mixed Group 6-9 Metal Acetylide Complexes -- VI. Mixed Group 10-12 Metal Acetylide Complexes -- VII. Other Mixed Metal Acetylide Complexes -- VIII. Abbreviations -- References -- Chapter 5. Transition Metal Organometallic Synthesis Utilising Diorganoiodine(III) Reagents -- I. Introduction -- II. Mechanisms of Reactions of Diorganoiodine(III) Reagents -- III. Organometallic Chemistry. , IV. Summary and Emerging Opportunities in Organometallic Chemistry -- Acknowledgments -- References -- Index -- Cumulative List of Contributors for Volumes 1-36 -- Cumulative Index for Volumes 37-55.

Note: Front cover -- Advances in Organometallic Chemistry -- Copyright page -- Contents -- Contributors -- Preface -- Chapter 1. Alkylidyne Complexes Ligated by Poly(pyrazolyl)borates -- I. Introduction -- II. Synthesis -- III. Structure and Spectroscopy -- IV. Reactivity -- V. Concluding Remarks -- References -- Chapter 2. Chemistry Surrounding Group 7 Complexes that Possess Poly(pyrazolyl)borate Ligands -- I. Introduction -- II. High Oxidation State Complexes -- III. Low Oxidation State Complexes -- IV. Summary -- References -- Chapter 3. The Organometallic Chemistry of Group 8 Tris(pyrazolyl)borate Complexes -- I. Introduction -- II. Iron Tris(pyrazolyl)borate Chemistry -- III. Ruthenium Tris(pyrazolyl)borate Chemistry -- IV. Osmium Tris(pyrazolyl)borate Chemistry -- V. Concluding Remarks -- Acknowledgements -- References -- Chapter 4. The Organometallic Chemistry of Group 9 Poly(pyrazolyl)borate Complexes -- I. Introduction -- II. Cobalt -- III. Rhodium and Iridium -- IV.Perspectives in C-H Activation and Catalysis -- V. Concluding Remarks -- Acknowledgements -- References -- Index -- Cumulative List of Contributors for Volumes 1-36 -- Cumulative Index for Volumes 37-56.

Note: Front Cover -- Advances in Organometallic Chemistry -- Copyright Page -- Contents -- Contributors -- Chapter 1: Phosphine-Boranes and Related Ambiphilic Compounds: Synthesis, Structure, and Coordination to Transition Metals -- I. Introduction -- II. Synthesis -- III. Structure -- IV. Coordination -- V. Reactivity and Catalytic Application -- VI. Recent and in Press Literature -- VII. Conclusion -- Acknowledgments -- References -- Chapter 2: The Organometallic Chemistry of Group 10 Poly(pyrazolyl)borate Complexes -- I. Introduction -- II. Nickel -- III. Palladium and Platinum -- IV. Perspectives: Catalysis and C-H Activation -- V. Concluding Remarks -- Acknowledgments -- References -- Subject Index -- Cumulative List of Contributors for Volumes 1-36.

Note: Front Cover -- Advances in Organometallic Chemistry -- Copyright -- Contents -- Contributor -- Chapter 1: Siloles: Part 1: Synthesis,Characterization, andApplications -- I. Introduction -- II. Background -- III. Synthetic approaches to siloles -- A. Reductive dimerization of 1,2-diarylalkynes (Curtis method) -- B. Intramolecular cyclization of dialkynylsilanes (Tamao method) -- C. 1,1-Organoboration of dialkynylsilanes (Wrackmeyer method) -- D. Methods that involve transition metals or transition metal catalysis -- 1. 1,4-Dihalobutadienes as precursors to siloles -- 2. Exchange of Zr in zirconacycles for Si (Fagan method) -- 3. Metal-catalyzed routes to siloles -- E. Less general methods and targeted syntheses -- 1. Silylenes and siloles by photolysis methods (siloles without CH substituents) -- 2. Lithium reagents and rearrangement of lithium reagents -- 3. Formation of unique siloles -- 4. Dehydrohalogenation or dehydrogenation of silacyclopentane or silacyclopentene -- IV. Modification of preformed siloles -- A. Reactions at the silicon center or at a substituent on silicon -- B. Reactions at a ring carbon center or a substituent at the ring carbon -- V. Oligomers and polymers containing silole units -- A. Oligo(1,1-siloles) -- B. Oligomers with siloles bridged by organic groups at the 1,1- or 2,5-positions -- C. Poly(1,1-siloles) and polymers with organic bridging groups at the 1,1-positions -- D. Siloles linked through ring carbon positions -- 1. Polysiloles with alkynyl or vinyl linkages -- 2. Siloles linked through other cyclic units -- E. Siloles as pendant groups in polymers -- VI. Siloles in OLEDS: Device fabrication and characteristics -- VII. Summary -- References -- Chapter 2: Siloles: Part 2: Silaindenes(Benzosiloles) and Silafluorenes(Dibenzosiloles): Synthesis,Characterization, andApplications -- I. Introduction -- II. Background. , III. Synthetic Approaches to Silaindenes (Benzosiloles) -- A. Routes to 1-silaindene featuring lithium intermediates -- B. Transition metal-mediated formation of 1-silaindenes -- C. Miscellaneous routes to 1-silaindenes -- 1. Lithium-tellurium and lithium-halogen exchange -- 2. 1-Silaindenes from o-silylsubstituted phenylalkynes -- D. Substitution at silicon or ring carbons of 1-silaindenes -- 1. Substitution at the silicon center in silaindenes -- 2. Substitution at a C2 or C3 center of a 1-silaindene -- E. 1-Silaindene oligomers, ladder oligomers, and polymers -- 1. Systems with two or more silaindene units -- 2. Ladder oligomers and associated polymers -- IV. Synthetic Routes to Silafluorenes (Dibenzosiloles) -- A. Routes to silafluorenes featuring lithium intermediates -- B. Transition metal-mediated routes and a Friedel-Crafts route to silafluorenes -- C. Unique systems and methods to silafluorenes -- 1. Heterasumanenes -- 2. Unexpected formation of silafluorenes -- D. Modification reactions of silafluorenes -- 1. Modification or reactions at the silicon center of silafluorenes -- a. Coupling of organometallic reagents and generation of anions from silafluorene precursors -- b. 9,9-Dihydrido-9H-silafluorene -- c. Pentaorganosilicates -- d. Exchange reactions -- 2. Reactions at a ring carbon center -- E. Oligomers and polymers that contain a silafluorene unit -- 1. Oligo(silafluorenes) and oligo(silafluorenes) linked through silicon or carbon -- 2. Ladder oligomers -- 3. Polymers containing silafluorene units -- V. Silicon-Bridged Benzene-Heteroarenes -- VI. Silicon-Bridged Bithiophenes -- A. Synthesis of dithienosiloles through lithium reagents -- B. Oligomers and polymers containing dithienosilole units -- 1. Oligomers -- 2. Homopolymers -- 3. Copolymers -- VII. Summary -- References.

Note: Cover -- Contents -- Contributors -- Intramolecular Interconversions in Cyclosilazane Chemistry: A Joint Experimental-Theoretical Study -- Summary -- Introduction -- Formation of Four-, Six- and Eight-Membered -Rings -- Dimerization of Iminosilenes -- Electrophilic 1,3-Silyl Group Migration -- Nucleophilic 1,3-Methanide-Ion Migration -- Cyclodisilazane Anions -- Cyclodisilazane Cations -- 2,2,4,4,6,6-Hexamethylcyclotrisilazane -- Isomeric Cyclotri- and Cyclodisilazanes, DFT Calculations -- Isomeric Cyclotri- and Cyclodisilazane-Anions and -Dianions, DFT Calculations -- Substitution Reactions -- Interconversion Reactions -- Equilibrium between Silyl-Substituted Cyclotri- and Isomeric Cyclodisilazane-Anions -- Position of the Si-N-Bond Cleavage, Formation of the Silyl-Bridged Cyclodisilazanes -- Disubstitution of HMCTS with Ring Contraction -- Ring Contraction, Methanide-Ion Migration and Formation of Bicyclic Compounds -- 2,2,4,4,6,6,8,8-Octamethylcyclotetrasilazane, OMCTS -- Conformers and Isomeric Compounds of OMCTS, DFT Calculations -- Substitution Reactions, Synthesis of Mono- and Disubstituted Eight-Membered Rings and Bicyclic Compounds -- Interconversion Reactions -- Structural Isomers of the Mono-Anion of OMCTS, DFT Calculations -- Experimental Results -- Ring Contractions of the Mono-Anion of OMCTS with Triorganyl Chlorosilanes and Borazines -- DFT Calculations, Structural Isomers of the Dianion of OMCTS -- Experimental Results -- Ring Contraction and Formation of Unsymmetrically Substituted Four-Membered Rings -- Outlook -- References -- Molecular Alumo-Siloxanes and Base Adducts -- Introduction -- Structures of Compounds of the General Composition (RSiO1.5)n(AlOX)m -- Structures of Compounds of the General Composition (R2SiO)n(AlOX)m -- General Reactions and Structures of Compounds Derived from (Ph2SiO)8[AlO(OH)]4. , Synthesis of (Ph2SiO)8[AlO(OH)]4 and reactions with water and ammonia -- Simple Base-Adducts of (Ph2SiO)8[AlO(OH)]4 -- Base-Adducts of (Ph2SiO)8[AlO(OH)]4 with Poly-Methylene-Diamines H2N(CH2)nNH2 -- Conclusions -- Acknowledgments -- References -- Progress in the Chemistry of Stable Disilenes -- Introduction -- Synthesis -- Acyclic Disilenes -- Cyclic Disilenes -- Cyclotetrasilenes -- Cyclotrisilenes -- Other Endocyclic Disilenes -- Exocyclic Disilenes -- Silicon-Based Dienes -- Tetrasila-1,3-diene -- Spiropentasiladiene -- Trisilaallene -- Disilynes -- Cations, Anions, and Radicals with SiSi Double Bonds -- Bonding and Structures -- An Overview of Si=Si Double Bonds -- Strain Energies of Cyclic Disilenes -- Molecular Structures -- Acyclic Disilenes -- Cyclic Disilenes -- Silicon-Based Dienes -- Disilyne -- Ionic Disilenes -- UV- vis Absorption and Fluorescence Spectra -- Acyclic Disilenes -- Cyclic Disilenes -- Silicon-Based Dienes -- Disilyne -- Ionic Disilenes -- Cyclic Voltammetry -- 29Si NMR Spectra -- Acyclic Disilenes -- Cyclic Disilenes -- Silicon-Based Dienes -- Disilyne -- Ionic Disilenes -- Vibrational Spectra -- Reactions and Mechanisms -- Unimolecular Reaction -- E,Z-Isomerization -- Dissociation into Two Silylenes -- 1,2-Migration of Substituents and Related Isomerizations -- Skeletal Isomerization of Cyclic Disilenes -- Oxidation and Reduction -- Oxidation -- Reduction -- 1,2-Addition of Water, Alcohols, and Ammonia -- Addition of Halogens and Haloalkanes -- Carbometallation and Hydrometallation -- Ene Reaction -- Cycloaddition -- [2+1] and [2+2] Cycloaddition -- [2+3] and [2+4] Cycloadditions -- Miscellany -- Disilene-Transition Metal Complexes -- Synthesis -- Bonding and Structure -- Reactions -- Conclusion -- Acknowledgment -- References -- Metallacycloalkanes - Synthesis, Structure and Reactivity of Medium to Large Ring Compounds. , Introduction -- Metallacyclopentanes -- Group 4 Metallacyclopentanes -- Titanium -- Zirconium -- Hafnium -- Group 5 Metallacyclopentanes -- Group 6 Metallacyclopentanes -- Chromium -- Molybdenum -- Tungsten -- Group 7 Metallacyclopentanes -- Manganese -- Rhenium -- Group 8 Metallacyclopentanes -- Group 9 Metallacyclopentanes -- Cobalt -- Rhodium -- Iridium -- Group 10 Metallacyclopentanes -- Nickel -- Palladium -- Platinum -- Metallacyclohexanes -- Group 4 Metallacyclohexanes -- Titanium -- Hafnium -- Groups 5, 6, 7 -- Group 8 Metallacyclohexanes -- Group 9 Metallacyclohexanes -- Rhodium -- Iridium -- Group 10 Metallacyclohexanes -- Metallacycloheptanes -- Groups 4, 5, 6, 7 -- Group 8 Metallacycloheptanes -- Group 9 Metallacycloheptanes -- Rhodium -- Group 10 Metallacycloheptanes -- Metallacyclooctanes and Larger Rings -- Groups 4, 5, 6, 7 and 9 -- Group 8 Metallacyclooctanes and Larger Rings -- Group 9 Metallacyclooctanes and Larger Rings -- Conclusion -- Acknowledgments -- References -- The Chemistry of Cyclometallated Gold(III) Complexes with C,N-Donor Ligands -- Introduction -- Synthesis of Five-Membered Ring Cycloaurated Complexes -- Direct Cycloauration Reactions -- Silver Ion-Assisted Cycloauration Reactions -- Transmetallation Reactions -- Complexes Containing Two Potentially Cycloaurating Ligands -- Miscellaneous Syntheses -- Unsuccessful Cycloauration Systems -- Related Compounds with Anionic Nitrogen Donor Ligands -- Synthesis of Six-Membered Ring Cycloaurated Complexes -- Direct Cycloauration Reactions -- Chemically Assisted Cycloauration Reactions -- Reactivity of Cycloaurated Complexes -- Phosphine Ligands -- Neutral Nitrogen Donor and Other Ligands -- Halide and Pseudohalide Ligands -- Carboxylate Derivatives -- Complexes with Ancillary Aryl Ligands -- Acetonyl Complexes -- Ligand Displacement Reactions of Pincer Complexes. , Bidentate Anionic Ligands with C-, N- and O-Donor Groups -- Bidentate Ligands with S-Donor Groups -- Reactions Involving Displacement of the Coordinated N-Donor Ligand -- With Halide and Cyanide Ligands -- With Dithiocarbamate Ligands -- With Thiosemicarbazone Ligands -- Reactions Involving Complete Displacement of the Cycloaurated Ligand -- Properties and Applications -- Biological Activity -- Electrochemical Properties -- Photophysical Properties -- Acknowledgments -- References -- Sterically Demanding Phosphinimides: Ligands for Unique Main Group and Transition Metal Chemistry -- Introduction -- Group 1: Lithium -- Group 2: Magnesium -- Group 4 -- Titanium -- Zirconium -- Group 5 -- Vanadium -- Tantalum -- Group 8: Iron -- Group 13 -- Boron -- Aluminum -- Group 14 -- Summary and Future Directions -- Acknowledgments -- References -- Transition Metal Complexes of Tethered Arenes -- Introduction -- Preparative Methods -- General Considerations -- Syntheses via Initial Arene Coordination (Scheme 1a) -- Syntheses via Initial Donor Atom Coordination (Scheme 1b) -- Syntheses via Intramolecular Construction of the Strap (Scheme 1c) -- Syntheses via Alkyne Condensation (Scheme 1d) -- Tethered Arene-Phosphine Complexes of Ruthenium(II) -- General Considerations -- Structural Features -- Reactivity -- Redox Behaviour -- Tethered Non-Benzenoid Aromatic Complexes -- Acknowledgments -- References -- Index -- Cumulative List of Contributors for Volumes 1-36 -- Cumulative Index for Volumes 37-54.

Note: Cover -- Advances in Organometallic Chemistry -- Copyright page -- TOCContents -- Preface -- CHChapter 1. Fully Condensed Polyhedral Oligosilsesquioxanes (POSS): From Synthesis to Application -- I. Introduction -- II. T2 Compounds -- III. T4 Compounds -- IV. T6 Compounds -- V. T8 Compounds -- VI. Syntheses, Properties, and Reactions of T10 Derivatives -- VII. T12, T14, and T16 Derivatives and Larger POSS Compounds -- VIII. Concluding Remarks -- Abbreviations -- Acknowledgments -- References -- CHChapter 2. Silyl Radicals in Chemical Synthesis -- I. Introduction -- II. Silyl Radicals -- III. Silanes as Radical-Based Reducing Agents -- IV. Silanes as Mediators of Consecutive Radical Reactions -- Radical Chemistry of Poly(hydrosilane)s -- Radical Chemistry on the Silicon Surfaces -- Conclusions -- References -- CHChapter 3. Advances in the Coordination Chemistry of Amidinate and Guanidinate Ligands -- I. Introduction -- II. General Aspects of Amidinate and Guanidinate Complexes -- III. Coordination Chemistry of Amidinate and Guanidinate Ligands -- IV. Special Aspects of Amidinate and Guanidinate Coordination Chemistry -- V. Amidinate and Guanidinate Complexes in Catalysis -- VI. Amidinate and Guanidinate Complexes in Materials Science -- VII. Future Outlook -- Acknowledgments -- References -- CHChapter 4. Equilibrium, Structural and Biological Activity Studies on [Organotin(IV)]n+ Complexes -- I. Introduction -- II. Physicochemical and Biological Methods for Study of Organotin(IV) Compounds -- III. Hydrolysis of [Organotin(IV)]nplus Cations -- IV. Interactions of [Organotin(IV)]n+ with Biological Molecules -- V. Applications -- VI. Conclusions -- Abbreviations -- Acknowledgments -- References -- IDXSubject Index -- Cumulative List of Contributors for Volumes 1-36 -- Cumulative Index for Volumes 37-57.

Note: Intro -- Advances in Organometallic Chemistry -- Copyright -- Contents -- Contributors -- Chapter One: Free Boroles: The Effect of Antiaromaticity on Their Physical Properties and Chemical Reactivity -- 1. Introduction -- 2. Structural and Electronic Characteristics: General Considerations -- 3. Early Work -- 4. Free Boroles: 4π-Electron Systems -- 4.1. Synthetic routes -- 4.2. Derivatizations -- 4.3. Stabilizing interactions -- 4.4. Structural and spectroscopic properties -- 4.5. HOMO-LUMO energies -- 4.6. Lewis acidity -- 5. Reactivity Patterns -- 5.1. Lewis acid-base adducts -- 5.2. Diels-Alder reactivity -- 5.3. Bond activation chemistry -- 5.4. Reduction chemistry -- 5.4.1. Electrochemistry of neutral boroles -- 5.4.2. Five π-electron systems -- 5.4.3. Six π-electron systems -- 5.4.4. Concluding remarks -- 6. Conclusions and Outlook -- Acknowledgments -- References -- Chapter Two: Recent Progress in the Chemistry of Metal Amidinates and Guanidinates: Syntheses, Catalysis and Materials -- 1. Introduction -- 2. General Aspects of Amidinate and Guanidinate Complexes -- 3. Amidinate and Guanidinate Complexes of Main Group Metals -- 3.1. Group 1 metal complexes: New starting materials -- 3.2. Group 2 metal complexes -- 3.3. Group 13 element amidinates and guanidinates -- 3.4. Group 14 element amidinates and guanidinates -- 3.5. Group 15 element amidinates and guanidinates -- 4. Amidinate and Guanidinate Complexes of the Early Transition Metals -- 4.1. Group 4 metal complexes -- 4.2. Group 5 metal complexes -- 4.3. Group 6 metal complexes -- 5. Amidinate and Guanidinate Complexes of the Middle and Late Transition Metals -- 5.1. Group 7 metal complexes -- 5.2. Group 8 metal complexes -- 5.3. Group 9 metal complexes -- 5.4. Group 10 metal complexes -- 5.5. Group11 metal complexes -- 5.6. Group 12 metal complexes. , 6. Amidinate and Guanidinate Complexes of the f-Elements -- 6.1. Lanthanide amidinates and guanidinates -- 6.1.1. Divalent lanthanide complexes -- 6.1.2. Trivalent lanthanide complexes -- 6.1.3. Tetravalent lanthanide complexes -- 6.2. Actinide amidinates and guanidinates -- 7. Amidinate and Guanidinate Complexes in Catalysis -- 7.1. Main group metal amidinate and guanidinate catalysis -- 7.2. Early transition metal amidinate and guanidinate catalysis -- 7.3. Middle and late transition metal amidinate and guanidinate catalysis -- 7.4. f-Element amidinate and guanidinate catalysis -- 7.4.1. Polymerization of simple olefins and dienes -- 7.4.2. Polymerization of polar monomers -- 7.4.3. Other reactions catalyzed by lanthanide amidinates and guanidinates -- 8. Amidinate and Guanidinate Complexes in Materials Science -- 8.1. Main group metal amidinate and guanidinate precursors -- 8.2. Early transition metal amidinate and guanidinate precursors -- 8.3. Middle and late transition metal amidinate and guanidinate precursors -- 8.4. Lanthanide amidinate and guanidinate precursors -- 9. Future Outlook -- Acknowledgments -- References -- Chapter Three: Structural Perspective on Aggregation of Alkali Metal Ions with Charged Planar and Curved Carbon π-Surfaces -- 1. Introduction -- 2. Polyarenes with Fused Six-Membered Rings -- 2.1. Naphthalene -- 2.2. Anthracene, dianthryl, and phenalenyl -- 2.3. Tetracene, pyrene, and perylene -- 2.4. Diphenyltetrabenzanthracene and rubrene -- 2.5. Coronene -- 3. Planar Polyarenes with Fused Five- And Six-Membered Rings -- 3.1. Pentalene -- 3.2. Indenyls -- 3.2.1. Aggregation with Li+ ions -- 3.2.2. Aggregation with other alkali metal ions -- 3.3. Fluorenyls -- 3.3.1. Complexes with Li+ ions -- 3.3.2. Complexes with Na+ ions -- 3.3.3. Complexes with K+ ions -- 3.3.4. Complexes with Rb+ and Cs+ ions -- 3.3.5. Bisfluorenyls. , 3.4. Indacene -- 3.5. Acenaphthylene -- 3.6. Dibenzopentalene -- 3.7. Indenofluorene and cyclopentaphenanthrene -- 3.8. Benzoindenofluorene and decacyclene -- 4. Bowl-Shaped Polyarenes -- 4.1. Coordination properties of buckybowls -- 4.2. Acepentalene and tribenzacepentalene -- 4.3. Corannulene -- 4.3.1. Monoanions -- 4.3.2. Dianions -- 4.3.3. Trianions -- 4.3.4. Tetraanions -- 4.3.5. Geometrical perturbations of corannulene core upon stepwise electron acquisition -- 5. Fullerene-Anions -- 6. Conclusions -- Acknowledgments -- References -- Index.

Note: Fron Cover -- Advances in Organometallic Chemistry -- Copyright -- Contents -- Contributors -- Chapter One: Homogeneous Organometallic Chemistry of Methane -- 1. Introduction -- 2. Inspiration: The Early Days of Hydrocarbon Activation -- 3. Oxidative Addition -- 3.1. Controlled oxidative addition -- 3.2. Alkane dehydrogenation -- 4. σ-Bond Metathesis -- 5. 1,2-Addition -- 6. Metalloradicals -- 7. 1,3-Addition -- 8. Electrophilic Carbene Insertion -- 9. Conclusions -- References -- Chapter Two: Supramolecular Self-assembly of Transition Metal Carbonyl Molecules Through M-CO(Lone Pair). . . π(Arene) Interactions -- 1. Introduction -- 2. Data Mining -- 3. Supramolecular Aggregation Based on M-CO(Lone Pair). . .π(Arene) Interactions -- 3.1. Motif A -- 3.2. Motif B -- 3.3. Motif C -- 3.4. Motif D -- 3.5. Motifs E, F, and G -- 3.6. Motifs H and I -- 3.7. Motif J -- 3.8. Motif K -- 4. Thio- and Selenocarbonyl Analogues -- 5. Strength and Correlations -- 6. Conclusions and Outlook -- Acknowledgments -- References -- Chapter Three: Metallabenzenes and Metallabenzenoids -- 1. Introduction -- 2. Synthetic Routes to Metallabenzenes and Metallabenzenoids -- 2.1. Metallacyclic ring expansion or contraction -- 2.1.1. Ring expansion of metallacyclopentadienes through insertion of one carbon atom -- 2.1.1.1. Migratory insertion involving a vinylidene ligand and a metallacyclopentadiene -- 2.1.1.2. Migratory insertion involving a carbene ligand and a metallacyclopentadiene -- 2.1.1.3. Migratory insertion involving a carbyne ligand and a metallacyclopentadiene -- 2.1.1.4. Migratory insertion involving a thiocarbonyl ligand and a metallacyclopentadiene -- 2.1.1.5. Migratory insertion involving a carbonyl ligand and a metallacyclopentadiene -- 2.1.2. Ring expansion of metallacyclobutenethiones or metallacyclobutadienes through insertion of two carbon atoms. , 2.1.2.1. Migratory insertion involving an ethyne and a metallacyclobutenethione -- 2.1.2.2. Migratory insertion involving an alkyne and a metallacyclobutadiene -- 2.1.3. Ring contraction of metallacycloheptatrienes -- 2.2. Addition to a metal substrate of a molecule or anion that contains the five carbon atoms of the impending metallabenzene -- 2.2.1. Reactions with the 2,4-dimethylpentadienide anion -- 2.2.2. Reactions with lithiated Z-3-(2-iodoethenyl)cyclopropenes -- 2.2.3. Reactions with 1,4-pentadiyne-3-ol and related compounds -- 2.2.3.1. Reactions with 1,4-pentadiyne-3-ol -- 2.2.3.2. Reactions with pent-1-en-4-yn-3-ols -- 2.2.3.3. Reactions with 1-phenylprop-2-yn-1-ol -- 2.3. Modification of six-membered metallacyclic rings -- 2.3.1. Reaction of osmabenzynes with nucleophiles -- 2.3.2. Modification of metallacyclohexadienes -- 2.4. Intramolecular coupling of the δ-carbon of one ligand with the carbon donor of an adjacent ligand -- 2.4.1. Coupling of CO with the lithiated δ-carbon atom of an adjacent ligand -- 2.4.2. Coupling of vinylidene with the δ-carbon atom of a butadienyl ligand -- 3. The Chemistry of Metallabenzenes and Metallabenzenoids -- 3.1. Electrophilic aromatic substitution -- 3.2. Nucleophilic aromatic substitution of hydrogen -- 3.2.1. Intermolecular nucleophilic aromatic substitution of hydrogen -- 3.2.2. Intramolecular nucleophilic aromatic substitution of hydrogen -- 3.3. π-Complexation of metal substrates to metallabenzenes -- 3.4. Rearrangement of metallabenzenes to cyclopentadienyl complexes -- 3.5. Cycloaddition reactions -- 3.6. Metallabenzene ring annulation -- 3.7. Reactions of metallabenzenes with protons -- 3.7.1. Proton addition -- 3.7.2. Ring cleavage by protons -- 3.8. Ancillary ligand substitution -- 3.9. Miscellaneous reactions -- 3.9.1. CO insertion -- 3.9.2. Oxidation of the metal. , 3.9.3. Osmanaphthalyne formation -- 3.9.4. Trans-esterification of a ring substituent -- 3.9.5. Cell cytotoxicity and anticancer properties -- 4. Structural and Spectroscopic Studies -- 4.1. Structural studies -- 4.2. Spectroscopic studies -- 5. Bonding in Metallabenzenes -- 5.1. Molecular orbital descriptions -- 5.2. Aromaticity in metallabenzenes -- 6. Concluding Remarks -- References -- Colour plate.