Description
Organometallic Compounds, Softcover reprint of the original 1st ed. 1968
Volume Two: The Transition Elements
Author: Green M. L.
Language: EnglishKeywords
chromium; copper; gold; manganese; metals; molybdenum; nickel; olefine; organometallic chemistry; palladium; platinum; rhodium; silver; titanium; transition metal
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Publication date: 11-2013
376 p. · 15.2x22.9 cm · Paperback
376 p. · 15.2x22.9 cm · Paperback
Description
/li>Contents
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to thank Messrs J. R. Sanders, W. E. Lindsell and M. G. Swanwick for helping to check the text and references and prepare indexes. Finally, I should like to thank my wife for the very considerable assis tance she has given me in the writing and production of this book. M. L. H. G. Contents Preface to the Third Edition, Volume Two Page v INTRODUCTION TO VOLUME TWO I Oassification I The IS-electron rule 2 (i) The basis of the I8-electron rule p. 4, (ii) Exceptions to the I8-electron rule p. 5 1. TWO-ELECTRON LIGANDS 7 A. Classification 7 B. The preparation of olefin-transition metal complexes 7 (a) Displacement of solvent ligands p. 9, (b) Preparations from metal carbonyls p. 9, (c) Less common preparative routes p. 11, Reductive olefination method p. 12 C. A molecular orbital description of the bonding in orga- metallic complexes 13 (a) General comments p. 13, (b) Symmetry considerations p. 13, (c) Energies of the molecular orbitals p. 14 D. A description of the bonding of 2-electron ligands to transition metals 14 E. General comments of 2-electron ligands 19 (a) Infrared studies p. 20, (b) Effect of olefin substituents p. 21, (c) The rotation of ethylene about the ligand-metal bond p. 22, (d) Chemical properties p. 23 F. Particular complexes of metals with 2-electron ligands 25 (a) Copper, silver and gold p. 25, Complexes with benzene p. 28, (b) Nickel, palladium and platinum p.
to Volume Two.- Classification.- The 18-electron rule.- (i) The basis of the 18-electron rule.- (ii) Exceptions to the 18-electron rule.- 1. Two-Electron Ligands.- A. Classification.- B. The preparation of olefin-transition metal complexes.- (a) Displacement of solvent ligands.- (b) Preparations from metal carbonyls.- (c) Less common preparative routes.- Reductive olefination method.- C. A molecular orbital description of the bonding in organo-metallic complexes.- (a) General comments.- (b) Symmetry considerations.- (c) Energies of the molecular orbitals.- D. A description of the bonding of 2-electron ligands to transition metals.- E. General comments of 2-electron ligands.- (a) Infrared studies.- (b) Effect of olefin substituents.- (d) The rotation of ethylene about the ligand-metal bond.- (d) Chemical properties.- F. Particular complexes of metals with 2-electron ligands.- (a) Copper silver and gold.- Complexes with benzene.- (b) Nickel palladium and platinum.- Trans effects.- (c) Rhodium iridium ruthenium osmium and rhenium.- (d) Miscellaneous.- 2. Three-Electron Ligands.- A. Preparation of ?-enyl complexes.- (a) From allyl Grignard reagents.- (b) From allyl halides and allyl alcohols.- (c) From olefins.- (d) From alienes.- B. The structure of ?-enyl complexes.- C. The ?-allyl metal bond.- D. Dynamic equilibria in allyl complexes.- E. The chemistry of particular ?-enyl complexes.- (a) Pure ?-allyl metal complexes.- (b) ?-Enyl complexes of nickel palladium and platinum.- (i) Cyclobutenyl complexes].- (ii) Cyclopentenylcomplexes.- (iii) Cyclo-propenyl complexes.- (c) ?-Enyl cobalt and rhodium complexes.- (d) Iron ?-enyl complexes.- (e) Miscellaneous.- 3. Four-Electron Ligands.- A. Some differences between unconjugated and conjugated olefin ligands.- B. The bonding of 4-electron ligands to transition metals.- (a) Cyclobutadiene complexes.- (b) Butadiene complexes.- C. Particular studies.- (a) Cyclobutadiene complexes.- (i) Preparation.- (ii) Properties.- (b) Cyclopentadiene complexes.- (c) Non-cyclic diene-metal complexes.- (d) Miscellaneous 4-electron ligands.- 4. Five-Electron Ligands.- A. Cyclopentadienyl metal complexes.- (a) Classification and nomenclature.- B. ?-Cyclopentadienyl transition metal complexes.- (a) Preparation.- (i) Reaction of alkali metal cyclopenta-dienides with metal complexes.- (ii) Reaction between cyclopentadiene and metal complexes.- (iii) Reaction between fulvenes and metal carbonyls.- (b) Bis-?-cyclo-pentadienyl transition metal complexes.- (i) Crystal structure.- (ii) Molecular structure.- (iii) Electronic structure.- (iv) The stability of bis-n-cyclopentadienyl complexes.- (v) The solubility properties of the cations [(?-C5H5) 2M]+.- (vi) Some chenical reactions of bis-n-cyclopentadienyl complexes.- (c) ?-Cyclopentadienyl complexes of uranium thorium and actinide metals.- C. Cyclopentadienide transition metal complexes.- (a) Manganocene.- (b) Ionic character in the bis-?-cyclo-pentadienyls.- (c) Rare earth cyclopentadienides.- D. The bonding in mono-?-cyclopentadienyl transition metal complexes.- (a) The bonding in metal-tricarbonyl groups.- E. ?-Cyclopentadienyl carbonyl complexes.- (a) Vanadium niobium and tantalum complexes.- (b) Complexes of chromium molybdenum and tungsten.- (c) Some ?-cyclopentadienyl iron carbonyl chemistry.- (d) Cobalt and rhodium complexes.- (e) Complexes of nickel and platinum.- (f) Ligand substitution reactions of ?-cyclopentadienyl manganese tricarbonyl.- F. ?-Cyclopentadienyl nitrosyl complexes.- G. Brief notes on binuclear ?-cyclopentadienyl complexes containing bridging ligands.- H. ?-Cyclopentadienyl hydride complexes.- I. ?-Cyclopentadienyl halides and oxides.- (a) ?-Cyclopentadienyl titanium halide chemistry and related topics.- (b) Vanadium niobium and tantalum complexes.- (c) Chromium molybdenum and tungsten complexes.- J. Other 5-electron ligands.- (a) ?-Cyclohexadienyl complexes.- (b) ?-Cyclohepta-dienyl complexes.- (c) Pentadienyl complexes.- K. The organic chemistry of ?-cyclopentadienyl transition metal complexes.- (a) Electronic effects in ferrocene.- (b) The participation of the iron atom in the chemistry of ferrocenes.- (i) Some mechanisms of electrophilic and radical substitution reactions.- (ii) The interaction of the iron atom with ring substituents 142: ?-Carbonium ion stabilization.- ?-Carbonium ion stabilization.- Weak hydrogen bonding by the iron atom.- (e) Trends in the chemistry of ferrocene ruthenocene and osmocene.- L. Some particular reactions.- (a) Acylation.- (b) Alkylation reactions.- (c) Aryla-tion reactions.- (d) Halogenation.- (e) Hydroxyl compounds.- (f) Metallation studies.- (g) Nitration and sulphonation.- (h) Amine derivatives.- (i) Carboxylic acid derivatives.- (j) Carboxaldehyde derivatives.- 5. Six-Electron Ligands.- A. Arene transition metal complexes.- (a) Preparation.- (i) Fischer’s reducing Friedel-Crafts method.- (ii) Cyclic polymerization of disubstituted acetylenes.- (iii) From aryl Grignard reagents.- (iv) From metal carbonyls.- (v) From substituted metal car-bonyls.- (b) Structural studies.- (c) The bonding in bis-?-arene complexes.- (d) The stability of bis-?-arene complexes.- (e) Some chemistry of bis-?-arene complexes.- (f) The stereochemistry of some arene metal carbonyls.- (g) Some reactions of arene metal carbonyls.- (h) Polynuclear complexes of the Group IV and Group V metals.- B. Olefin 6-electron ligands.- C. Transition metal complexes containing ?-bonded heterocyclic ligands.- 6. Seven-Electron Ligands Mixed Sandwich Complexes Related Azulene Derivatives and Cyclo-Octatetraene Complexes.- A. 7-Electron ligands.- (a) Preparation of ?-cycloheptatrienyl complexes.- (b) Structure.- (c) The chemistry of ?-cycloheptatrienyl complexes.- Ring contraction and expansion reactions.- B. Mixed sandwich complexes.- C. Metal complexes formed from azulenes.- D. Cyclo-octatetraene complexes.- 7. One-Electron Ligands.- I.1. Hydrocarbon alkyl and aryl complexes.- A. General preparative methods.- (a) From Grignard reagents and organoalkali metal derivatives.- (b) From complex metal anions and organic halides.- (c) From metal hydrides.- (d) Miscellaneous.- B. General chemical properties.- (a) Stability.- (b) Cleavage reactions of the metal-carbon bond.- (c) Insertion reactions.- C. The nature of interactions between transition metals and o-bonded organic substituents.- (a) Transition metal-?-interactions.- Metal carbene complexes.- (b) Transition metal-?-interactions.- (c) The possible nature of the ?-effect.- D. The bonding of 1-electron ligands to transition metals.- (a) Metal-carbon single bonds.- (b) Metal-carbon multiple bonds.- (i) Metal aryls.- (ii) Metal ‘carbenes’.- E. The stability of metal-?-organo complexes.- (a) Introduction.- (b) The thermodynamic stability of metal-?-organo complexes.- (c) The kinetic stability of metal-?-organo complexes.- The kinetic stability of organic complexes of square-planar nickel palladium and platinum.- F. Tertiary phosphine transition metal-alkyl and -aryl complexes and related compounds.- (a) Nickel, palladium and platinum.- (i) Nickel.- (ii) Palladium.- (iii) Platinum.- (b) Cobalt rhodium and iridium.- (c) Iron and ruthenium.- (d) Miscellaneous.- G. ?-Cyclopentadienyl carbonyl complexes.- (a) ?-Cyclopentadienyl iron dicarbonyl derivatives.- (b) ?-Cyclopentadienyltricarbonyl complexes of chromium molybdenum and tungsten.- Cobalt rhodium and nickel.- H. Carbonyl alkyl aryl and acyl complexes.- (a) Manganese and rhenium.- (b) Cobalt.- (c) Platinum.- (d) Miscellaneous.- I. Bis-?-cyclopentadienyl alkyl and aryl complexes.- J. ?-Bonded organic derivatives of particular metals.- (a) Pure alkyl and aryl complexes and alkyl halides of titanium vanadium niobium tantalum and manganese.- (i) Titanium complexes.- (ii) Vanadium niobium and tantalum.- (iii) Manganese.- (b) Alkyl and aryl complexes of chromium.- (i) Neutral alkyl and aryl chromium complexes.- (ii) Anionic alkyl and aryl chromium complexes.- (iii) Penta-aquo chromium(III) alkyls.- (c) Cobalt(III) complexes with ?-bonded ligands.- Vitamin B12chemistry.- (d) Alkyl complexes of platinum (IV).- Trimethylplatinum (IV) complexes.- Cyclopropane complexes of platinum.- (e) Alkyls and aryls of copper silver and gold.- (i) Copper.- (ii) Silver.- (iii) Gold.- I.2 Transition metal-acyl complexes.- A. The carbonylation of pentacarbonylmanganese alkyls and aryls.- B. Related carbonylation reactions.- C. The metal-acyl bond.- I.3. ?-Cyclopentadienyl complexes.- II. Transition metal fluorocarbon complexes.- A. Preparation 263 (a) Fromperfluoroacyl halides.- (b) From perfluoroalkyl halides.- (c) From perfluoro-olefins and related compounds.- (d) From perfluoro Grignard reagents and lithium compounds.- B. The properties of perfluoro-alkyl and -aryl transition metal complexes.- C. The metal-perfluorocarbon bond.- III. Transition metal acetytides and alkynyls.- A. Complex acetylides.- B. ‘Pure’ metal acetylides and alkynyls.- C. Alkynyl-transition metal tertiary phosphines and related complexes.- (a) Nickel palladium and platinum.- (b) Copper silver and gold.- (c) Miscellaneous.- 8. Organometallic Complexes Formed From Acetylenes.- A. Monoacetylene, mononuclear complexes: acetylenes as 2-elec-tron ligands.- B. Monoacetylene binuclear complexes: acetylenes as 4-electron ligands.- C. Monoacetylene trinuclear complexes.- D. Monoacetylene tetranuclear complexes.- E. Bis-acetylene mononuclear complexes.- (a) Cyclopentadienone and quinone metal complexes.- (i) Preparation.- (ii) Properties of cyclopentadienone metal complexes.- (b) Quinone complexes.- (c) Ferra-cyclopentadiene complexes.- F. Bis-acetylene trinuclear complexes.- G. Tris-acetylene mononuclear complexes.- H. Tris-acetylene binuclear complexes.- I. Miscellaneous.- 9. The Role of Organotransition Metal Complexes in Some Catalytic Reactions.- A. Some chemistry of transition metal hydride complexes.- (a) Preparation.- (b) The nature of the metal-hydrogen bond.- (c) Properties.- (d) Bridging hydrogen systems.- B. Some catalytic reactions which involve hydrogen transfer: isomerization reactions.- C. Homogeneous hydrogenation of olefins and acetylenes.- (a) Catalysis by cobalt cyanide solutions.- D. Some dimerization oligomerization and polymerization reactions of olefins and acetylenes.- (a) Dimerization reactions.- (b) Trimerization reactions.- (i) The trimerization of acetylenes.- (ii) The trimerization of butadiene and related reactions catalysed by some ?-allyl metal complexes.- (iii) Other nickel catalysts.- (c) Some comments on polymerization of olefins by Ziegler catalysts.- (d) Some mechanisms of olefin polymerization by Ziegler catalysts.- E. Hydroformylation and related carhonylation reactions.- F. Some general comments on the relationship between heterogeneous and homogeneous transition metal catalysts.- G. Miscellaneous.- (a) The oxidation of ethylene to acetaldehyde.- (b) Some reactions catalysed by copper and its derivatives.- (c) Nitrogen fixation.- Author.- Subject.- Crystal Structures>.
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