THE ORGANOMETALLIC CHEMISTRY OF THE TRANSITION METALS

By JOHN SANCHEZ

CONTENTS INTRODUCTION WERNER COMPLEXES, THE TRANS EFFECT, SOFT VERSUS HARD LIGANDS, THE CRYSTAL FIELD, THE LIGAND FIELD, BACK BONDING, ELECTRONEUTRALITY, TYPES OF LIGAND, GENERAL PROPERTIES OF ORGANOMETALLIC COMPLEXES THE 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 COORDINATION, METAL ALKYLS, ARYLS, AND HYDRIDES AND RELATED ?-BONDED LIGANDS TRANSITION METAL ALKYLS AND ARYLS, RELATED ?-BONDED LIGANDS, METAL HYDRIDE COMPLEXES, ? COMPLEXES, BOND STRENGTHS FOR CLASSICAL ?-BONDING LIGANDS, CARBONYLS, PHOSPHINE COMPLEXES, AND LIGAND SUBSTITUTION REACTIONS METAL 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 SUBSTITUTION, COMPLEXES OF ?-BOUND LIGANDS ALKENE AND ALKYNE COMPLEXES, ALLYL COMPLEXES, DIENE COMPLEXES, CYCLOPENTADIENYL COMPLEXES, ARENES AND OTHER ALICYCLIC LIGANDS, METALACYCLES AND ISOELECTRONIC AND ISOLOBAL REPLACEMENT, STABILITY OF POLYENE AND POLYENYL COMPLEXES, OXIDATIVE ADDITION AND REDUCTIVE ELIMINATION CONCERTED ADDITIONS, SN2 REACTIONS, RADICAL MECHANISMS, IONIC MECHANISMS, REDUCTIVE ELIMINATION, ?-BOND METATHESIS, OXIDATIVE COUPLING AND REDUCTIVE CLEAVAGE, INSERTION AND ELIMINATION REACTIONS INVOLVING CO, INSERTIONS INVOLVING ALKENES, OTHER INSERTIONS, ?, ?, ? , AND ? ELIMINATION, NUCLEOPHILIC AND ELECTROPHILIC ADDITION AND ABSTRACTION NUCLEOPHILIC ADDITION TO CO, NUCLEOPHILIC ADDITION TO POLYENE AND POLYENYL LIGANDS, 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 COMPLEXES, HOMOGENEOUS CATALYSIS ALKENE ISOMERIZATION, ALKENE HYDROGENATION, ALKENE HYDROFORMYLATION, HYDROCYANATION OF BUTADIENE, ALKENE HYDROSILATION AND HYDROBORATION, COUPLING REACTIONS, SURFACE AND SUPPORTED ORGANOMETALLIC CATALYSIS, PHYSICAL 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 METHODS, METAL–LIGAND MULTIPLE BONDS CARBENES, CARBYNES, BRIDGING CARBENES AND CARBYNES, N-HETEROCYCLIC CARBENES, MULTIPLE BONDS TO HETEROATOMS, APPLICATIONS OF ORGANOMETALLIC CHEMISTRY ALKENE METATHESIS, DIMERIZATION, OLIGOMERIZATION, AND POLYMERIZATION OF ALKENES, ACTIVATION OF CO AND CO2, CH ACTIVATION, ORGANOMETALLIC MATERIALS AND POLYMERS, CLUSTERS AND THE METAL–METAL BOND STRUCTURES, THE ISOLOBAL ANALOGY, SYNTHESIS, REACTIONS, GIANT CLUSTERS AND NANOPARTICLES, GIANT MOLECULES, APPLICATIONS TO ORGANIC SYNTHESIS METAL 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 MOLECULES, PARAMAGNETIC, HIGH-OXIDATION-STATE, AND HIGH-COORDINATION-NUMBER COMPLEXES MAGNETISM AND SPIN STATES, POLYALKYLS, POLYHYDRIDES, F -BLOCK COMPLEXES, BIOORGANOMETALLIC CHEMISTRY INTRODUCTION, COENZYME B12, NITROGEN FIXATION, NICKEL ENZYMES, BIOMEDICAL APPLICATIONS, USEFUL TEXTS ON ALLIED TOPICS MAJOR REACTION TYPES SOLUTIONS TO PROBLEMS