Crabtree R.H. The Organometallic Chemistry Of The Transition Metals

4th edition. — John Wiley & Sons Inc., 2005. - 546 p.
Organometallic compounds, with their metal-carbon bonds, lie at the interface between classical organic and inorganic chemistry in dealing with the interaction between inorganic metal species and organic molecules. In the related metal-organic compound area, in contrast, the organic fragment is bound only by metal-heteroatom bonds.
The organometallic field has provided a series of important conceptual insights, surprising structures, and useful catalysts both for industrial processes and for organic synthesis. Many catalysts are capable of very high levels of asymmetric induction in preferentially forming one enantiomer of a chiral product. The field is beginning to make links with biochemistry with the discovery of enzymes that carry out organometallic catalysis. Ideas drawn from organometallic chemistry have helped interpret the chemistry of metal and metal oxide surfaces, both key actors in heterogeneous catalysis. The field is also creating links with the chemistry of materials because organometallic and metal-organic compounds are increasingly preferred as the precursors for depositing materials on various substrates via thermal decomposition of the metal compound. Nanoscience and nanotechnology are also benefiting with the use of such compounds as the most common precursors for nanoparticles. These small particles of a metal or alloy, with properties quite unlike the bulk material, are finding more and more useful applications in electronic, magnetic, or optical devices or in sensors.
This book should be helpful not only to advanced research chemists, but also for teaching this chemistry to younger students in a comprehensive and modern way.Werner Complexes
The Trans Effect
Soft Versus Hard Ligands
The Crystal Field
The Ligand Field
Back Bonding
Electroneutrality
Types of LigandGeneral Properties of Organometallk ComplexesThe 18-Electron Rule
Limitations of the 18-Electron Rule
Electron Counting in Reactions
Oxidation State
Coordination Number and Geometry
Effects of Complexation
Differences between Metals
Outer-Sphere CoordinationMetal Alkyls, Aryls, and Hydrides and Related σ-Bonded LigandsTransition Metal Alkyls and Aryls
Related σ-Bonded Ligands
Metal Hydride Complexes
σ Complexes
Bond Strengths for Classical σ-Bonding LigandsCarbonyls, Phosphine Complexes, and Ligand Substitution ReactionsMetal Complexes of CO, RNC, CS, and NO
Phosphines and Related Ligands
Dissociative Substitution
Associative Mechanism
Redox Effects, the I Mechanism, and Rearrangements in Substitution
Photochemical Substitution
Steric and Solvent Effects in SubstitutionComplexes of π-Bound LigandsAlkene and Alkyne Complexes
Allyl Complexes
Diene Complexes
Cyclopentadienyl Complexes
Arenes and Other Alicyclic Ligands
Metalacycles and Isoelectronic and Isolobal Replacement
Stability of Polyene and Poiyenyl ComplexesOxidative Addition and Reductive EliminationConcerted Additions
S_N2 ReactionsRadical Mechanisms
Ionic Mechanisms
Reductive Elimination
σ-Bond Metathesis
Oxidative Coupling and Reductive CleavageInsertion and EliminationReactions Involving CO
Insertions Involving Alkenes
Other Insertions
α, β, γ, and δ EliminationNucleophilic and Electrophilic Addition and AbstractionNucleophilic Addition to CO
Nucleophilic Addition to Polyene and Polyenyl Ugands
Nucleophilic Abstraction in Hydrides, Alkyls, and Acyls
Electrophilic Addition
Electrophilic Abstraction of Alkyl Groups
Single-Electron Transfer Pathways
Reactions of Organic Free Radicals with Metal ComplexesHomogeneous CatalysisAlkene Isomerization
Alkene Hydrogenation
Alkene Hydroformylation
Hydrocyanation of Butadiene
Alkene Hydrosilation and Hydroboration
Coupling Reactions
Surface and Supported OrganometalHc CatalysisPhysical Methods in Organometallic Chemistry
Isolation
¹H NMR Spectroscopy
¹³C NMR Spectroscopy
³¹P NMR Spectroscopy
Dynamic NMR
Spin Saturation Transfer
T₁ and the Nuclear Overhauser Effect
Isotopic Perturbation of Resonance
IR Spectroscopy
Crystallography
Other MethodsMetal-Ligand Multiple BondsCarbenes
Carbynes
Bridging Carbenes and Carbynes
N-Heterocyclic Carbenes
Multiple Bonds to HeteroatomsApplications of Organometallic ChemistryAlkene Metathesis
Dimerization, Oligomerization, and Polymerization of
Alkenes
Activation of CO and CO₂
CH Activation
Organometallic Materials and PolymersClusters and the Metal-Metal BondStructures
The Isolobal Analogy
Synthesis
Reactions
Giant Clusters and Nanoparticles
Giant MoleculesApplications to Organic SynthesisMetal Alkyls Aryls, and Hydrides
Reduction, Oxidation, and Control of Stereochemistry
Protection and Deprotection
Reductive Elimination and Coupling Reactions
Insertion Reactions
Nucleophilic Attack on a Ligand
Heterocycles
More Complex MoleculesParamagnetic. High -Oxidation-State, and High-Coordination-Number ComplexesMagnetism and Spin States
Polyalkyls
Polyhydrides
Cyclopentadienyl Complexes
f-Block ComplexesBioorganometallic ChemistryCoenzyme B12
Nitrogen Fixation
Nickel Enzymes
Biomedical ApplicationsUseful Texts on Allied Topics

Major Reaction Types

Solutions to Problems

Index