CONTENTS PART I STRUCTURES OF THE TRANSITION-METAL COMPLEXES

Transcription

1 CONTENTS Introduction Organization of the text Frontiers of organometallic chemistry Situation of the book with respect to teaching Reference books and other selected references... 3 History of organometallic chemistry : The first complexes : Grignard, Sabatier, and catalysis in Germany : The discovery of ferrocene and the boom of organometallic chemistry : The discovery of multiple metal-carbon bonds and the golden age of catalysis : Activation of C-H bonds in hydrocarbons, -bond metathesis and H 2 as a ligand Current trends PART I STRUCTURES OF THE TRANSITION-METAL COMPLEXES Chapter 1 - Monometallic transition-metal complexes The ligands The characteristics of the transition-metal in the complexes Hapticity of the ligands and linear writing of the complex formulas The 18-electron rule : tendencies and exceptions Bonding between the transition metal and the -acceptor (CO, C 2 H 4 ) and -donor ligands (halogeno, alkoxy, amino) Molecular orbital diagrams Summary and Exercises Chapter 2 - Bimetallic transition-metal complexes and clusters The metal-metal bond in bimetallic complexes Types of molecular magnetism Clusters The isolobal analogy Summary and Exercises... 76

2 VIII ORGANOMETALLIC CHEMISTRY AND CATALYSIS PART II THE STOICHIOMETRIC REACTIONS OF TRANSITION-METAL COMPLEXES Chapter 3 - Redox reactions, oxidative addition and -bond metathesis Outer-sphere electron transfer Inner-sphere electron- and atom transfer Oxidative addition, reductive elimination and -bond metathesis Summary and Exercises Chapter 4 - Reactions of nucleophiles and electrophiles with complexes Nucleophilic reactions Reactions of electrophiles Summary and Exercises Chapter 5 - Ligand substitution reactions Introduction Pairwise mechanisms Electron-transfer-chain and atom-transfer-chain mechanisms Substitution of XL n ligands (n = 0-2) Summary and Exercises Chapter 6 - Insertion and extrusion reactions Introduction CO 1,1 migratory insertion Methylene insertion and extrusion , 2 migratory insertion of alkenes and alkynes into M-H bonds Insertion of alkenes into metal-alkyl bonds and the reverse reaction: C-C activation by -alkyl elimination and -elimination Summary and Exercises PART III THE MAIN FAMILIES OF ORGANOMETALLIC COMPLEXES Chapter 7 - Metal carbonyls and complexes of other monohapto L ligands Introduction Syntheses Binding modes Reactions Ligands isoelectronic to CO: CNR, CS, CSe, N 2 and NO Dioxygen O Phosphanes Weak L ligands and their role to generate organometallic Lewis acids Summary and Exercises...172

3 CONTENTS IX Chapter 8 - Metal-alkyl and -hydride complexes and other complexes of monohapto X ligands Different types of sp 3 metal-carbon bonds Stability of metal-alkyl complexes Synthesis of metal-alkyl complexes Properties of metal-alkyl complexes Metallocycles Metal-aryl, -vinyl, -alkynyl, -silyl, and -stannyl complexes Metal-hydrides and the dihydrogen ligand Alkoxy and amido complexes Summary and Exercises Chapter 9 - Metal-carbene and -carbyne complexes and multiple bonds with transition metals Metal-carbene complexes Metal-carbyne complexes Multiple bond between a heteroatom and a transition metal: oxo, imido, phosphinidene and nitrido ligands Summary and Exercises Chapter 10 - complexes of mono- and polyenes and enyls Metal-olefin complexes Metal-diene complexes and analogues Metal-alkyne complexes Allyl complexes Polyenyl complexes Arene complexes Summary and Exercises Chapter 11 - Metallocenes and sandwich complexes Structure of the metallocenes Redox properties of the sandwich metallocenes Metallocene synthesis Chemical properties of metallocenes Triple- and multiple-decker sandwich complexes Non-sandwich metallocenes derivatives Metal-bis-arene sandwich complexes Cylopentadienyl-metal-arene complexes Summary and Exercises...287

4 X ORGANOMETALLIC CHEMISTRY AND CATALYSIS Chapter 12 - Ionic and polar metal-carbon bonds: alkali and rare-earth complexes Introduction Organometallic complexes of alkali metals Grignard reagents The scandium, ytrium, lanthanides and actinides complexes Summary and Exercises Chapter 13 - Covalent chemistry of the organoelements of frontier (11, 12) and main (13-16) groups Introduction Group 11 (Cu, Ag, Au) Group 12 (Zn, Cd, Hg) Group 13 (B, Al, Ga, In, Tl) Group 14 (Si, Ge, Sn, Pb) Group 15 (As, Sb, Bi) Group 16 (Se, Te) Summary and Exercises PART IV CATALYSIS Introduction to catalysis Chapter 14 - Hydrogenation and hydroelementation of alkenes Hydrogenation of olefins Asymmetric hydrogenation Hydroboration of olefins Hydrocyanation of olefins Hydroamination of olefins and alkynes Summary and Exercises Chapter 15 - Transformations of alkenes and alkynes Ziegler-Natta-type olefin polymerization Metathesis of alkenes, alkynes and cycloalkenes Olefin dimerization and oligomerization Olefin isomerization Summary and Exercises...392

5 CONTENTS XI Chapter 16 - Oxidation of olefins Historic introduction and radical-type oxidation Ethylene oxidation to acetaldehyde: Wacker process Epoxidation of olefins Hydroxylation by metal-oxo complexes Phase-transfer catalysis in oxidation chemistry Summary and Exercises Chapter 17 - C-H activation and functionalization of alkanes and arenes Introduction Alkanes and cycloalkanes Aromatics Summary and Exercises Chapter 18 - Carbonylation and carboxylation reactions Carbonylation of methanol: Monsanto process Olefin hydroformylation: oxo process Carbonylation of alkenes and alkynes in the presence of a nucleophile: the Reppe reaction Carbonylation of aryl halides in the presence of a nucleophile Catalysis of CO 2 transformation Summary and Exercises Chapter 19 - Bio-organometallic chemistry: enzymatic catalysis Introduction Cobalamin: co-enzyme vitamin B Biological redox mediators Examples of oxido-reductase enzymes: the mono-oxygenases Nitrogen fixation by nitrogenase enzyme Nickel enzymes Summary and Exercises Chapter 20 Heterogeneous catalysis Introduction Concepts of heterogeneous catalysis CO and CO 2 hydrogenation and Fischer-Tropsch chemistry Transformation of hydrocarbons Metathesis of alkanes, alkenes and alkynes Oxidation of hydrocarbons Nanoparticle catalysis: the fast growing frontier between homogeneous and heterogeneous catalysis Summary and Exercises...485

6 XII ORGANOMETALLIC CHEMISTRY AND CATALYSIS PART V APPLICATIONS IN ORGANIC SYNTHESIS Chapter 21 - Organometallic complexes in organic synthesis Examples of applications Protection and stabilization of unsaturated organic derivatives and fragments Nucleophilic and electrophilic reactions on hydrocarbon ligands General methods of C-C bond formation using the oxidative addition of an organic halide or a related electrophile Extension of palladium catalysis to the formation of C-O and C-N bonds Oxidative coupling reactions of alkynes with other unsaturated fragments for the formation of cyclic and heterocyclic compounds Metal-carbene complexes in organic synthesis Examples of asymmetric catalysis Summary and Exercises Answers to exercises References Abbreviations Index Atomic weights of the elements Periodic table of the elements...611

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