Organotransition Metal Chemistry

Transcription

1 Organotransition Metal Chemistry From Bonding to Catalysis John R Hartwig UNIVERSITY OF ILLINOIS URBANA-CHAMPAIGN University Science Books Mill Valley, California

2 Contents Chapter 1. Structure and Bonding General Properties of the Ligands Classification of Ligands as Dative or Covalent, Neutral or Anionic, Even- or Odd-Electron, L-Type or X-Type Classification by Number of Electrons Donated to the Metal n-bonded Ligands Combinations of <r- and ir-donors Cationic Ligands Properties of the Metal Oxidation State The Relationship Between Oxidation State and the Number of d-electrons Trends in the Properties of Transition Metals Trends in Ionization Potentials Trends in Size Trends in Bond Strengths Metal-Ligand Complexes Electron Counting The 18-Electron Rule Metal-Metal Bonding and Electron Counting in Polynuclear Complexes Geometries of Transition Metal Complexes Isoelectronic and Isolobal Analogies Molecular Orbitals for Transition Metal Complexes u-bonding in Organotransition Metal Complexes TT-Bonding ofco and its Analogs Tr-Bonding of Carbene and Carbyne Complexes n:-bonding in Olefin Complexes Tr-Bonding with Other Unsaturated Ligands ir-donor Ligands 22 References and Notes 26 Chapter 2. Dative Ligands Introduction Carbon Monoxide and Related Ligands Properties of Free Carbon Monoxide Types of Metal Carbonyl Complexes Models for CO Binding: Backbonding Evidence for Backbonding Carbonyls 30 Introduction of in Terminal Infrared and X-Ray Diffraction Data for Complexes with Bridging Carbonyls Thermodynamics of the M-CO Bond Isoelectronic Analogs of CO: Isocyanides and Thiocarbonyls Dative Phosphorus Ligands Congeners 33 and Heavier Tertiary Phosphines and Related Ligands Chelating Phosphines Properties of Free Phosphines Properties of Phosphine Complexes Bonding and Electronic Properties Steric Properties Effects of Phosphine Steric and Electronic Properties on Structure and Reactivity Pathways for the Decomposition of Phosphorus Ligands NMR Spectroscopic Properties of Phosphines Heavier Congeners of Phosphorus Ligands Carbenes Classes of Free and Coordinated Carbenes Properties of Free Carbenes Properties of Carbene Complexes Bonding of Carbenes Spectroscopic Characteristics of Carbene Complexes Transition Metal Carbyne Complexes Bonding and Structure of Carbyne Complexes Spectroscopic Characteristics of Carbyne Complexes Organic Ligands Bound Through More than One Atom Olefin Complexes Stability ofmetal-olefin Complexes 47 vii

3 viii CONTENTS Structures of Metal-Olefin Complexes Structural Changes Upon Binding Orientation of Coordinated Olefins Spectral Properties ofmetal-olefin Complexes Alkyne Complexes Structural Characteristics ofalkyne Complexes 51 2, Physical and Chemical Properties ofalkyne Ligands Complexes of Organic Carbonyl Compounds Ti6-Arene and Related Complexes Complexes of Ligands Bound Through N,0 and S Neutral Nitrogen Donor Ligands Amine Complexes Pyridine and Imine Complexes Dinitrogen Complexes Complexes ofneutral Oxygen Donors Complexes ofneutral Sulfur Donors Sigma Complexes Overview of Sigma Complexes Dihydrogen Complexes Properties that Lead to Stable H2 Complexes Spectroscopic Signatures ofh2 Complexes Reactivity cfh2 Complexes Alkane and Silane Complexes Stability Relative to Hz Complexes Evidence for Alkane Complexes Intramolecular Coordination ofaliphatic C-H Bonds (Agostic Interactions) 71 References and Notes 73 Chapter 3. Covalent (X-Type) Ligands Bound Through Metal-Carbon and Metal-Hydrogen Bonds Introduction Transition Metal Hydrocarbyl Ligands Alkyl Ligands (Written with Prof. Jack R. Norton) History of Transition Metal-Alkyl Complexes Thermodynamic Properties ofm-alkyl Bonds Synthesis ofmetal-alkyl Complexes Synthesis of Alkyl Complexes by Transmetallation Synthesis of Alkyl Complexes by Alkylation Synthesis of Alkyl Complexes by Other Methods Selected Reactions ofmetal-alkyl Complexes Aryl, Vinyl, and Alkynyl Complexes (Written with Prof. Jack R. Norton) Synthesis of Complexes Containing Terminal Aryl Ligands Complexes with Bridging Aryl Ligands Properties ofmetal-aryl Complexes Vinyl Complexes (Written with Prof. Jack R. Norton) Alkynyl Complexes Enolate Complexes (Written with Prof. Erik J. Alexanian) Overview Structure of Enolate Complexes Spectral Features of Enolate Complexes Synthesis of Enolate Complexes Cyanide Complexes (Written with Prof. Jesse W. Tye) Overview Properties of the Free Molecule Structures and Electron Counting of Metal- Cyanide Complexes Thermodynamics of M-CN Linkages Spectral Features of M-CN Complexes Synthesis of CN~ Complexes Allyl, T 3-Benzyl, Pentadienyl, and Trimethylenemethane Ligands (Written with Dr. Mark J. Pouy) Allyl Ligands Overview Structures ofallyl Ligands Dynamics ofmetal-allyl Complexes Synthesis of tt-allyl Complexes Reactions ofallyl Complexes r,3-benzyl Complexes Higher Anionic ir-ligands ^-Trimethylenemethane (TMM) Complexes Cyclopentadienyl and Related Compounds (Written with Prof. Jack R. Norton) Overview Bonding and Thermodynamics of Cp Ligands 111

4 CONTENTS ix Synthesis of Ti5-Cyclopentadienyl Complexes Examples of Substituted Cyclopentadienyl Ligands Ansa Metallocenes Types of Cyclopentadienyl Complexes Cp^A and Their Permethyl Derivatives Cp*M Metallocenes Cpjtf. and their Permethyl Derivatives Cp*M Structures of "Sandwich Complexes" Bent Metallocenes Cp^AL^and Related Compounds "Half-Sandwich" Compounds CpML 117 y OtherModes ofbinding ofcyclopentadienyl Ligands Ligands That Are Electronically Similar to the Cyclopentadienyl Ligand Reactions of Cyclopentadienyl Complexes Hydride Ligands (Written by Prof. Jack R. Norton) Structural Features Terminal Hydrides Bridging Hydrides Spectroscopic Properties Synthesis of Metal-Hydride Complexes From Hydrogen By Protonation From Main Group Hydrides From Other Reagents Acidities of Hydride Complexes Strength of M-H Bonds Hydricities Hydrogen Bonding 136 References and Notes 137 Chapter 4. Covalent (X-Type) Ligands Bound Through Metal-Heteroatom Bonds Overview and Scope Complexes Containing Metal-Nitrogen Metal-Amido Complexes 147 Bonds Late-Metal-Amido Complexes (Written with Prof. Pinjing Zhao) Overview of Metal-Amido Complexes of the Late Transition-Metals Bonding of Late-Metal-Amido Complexes Thermodynamic Properties of Late-Metal-Amido Complexes Spectral Properties of Late-Metal- Amido Complexes Synthesis of Late-Metal-Amido Complexes Reactivity of Late-Metal-Amido Complexes Amido Complexes of the Early Transition Metals (Written with Prof. Seth B. Herzon) Overview Thermodynamic Properties of Early- Metal-Amido Complexes Synthesis of Early-Metal-Amido Complexes Reactivity of Early-Metal-Amido Complexes Amidate and Amidinate Complexes of the Early Transition Metals (Written with Prof. Seth B. Herzon) Complexes of Anionic Nitrogen Heterocycles (Written with Prof. Jianrong (Steve) Zhou) Overview Metal-Azolyl Bonding Synthesis ofmetal-azolyl Complexes Reactivity of Metal-Azolyl Complexes Nitrosyl Complexes (Written with Prof. Jesse W. Tye) Overview Properties of the Free Molecule Structures and Electron Counting of Metal-Nitrosyl Complexes Thermodynamics ofm-no linkages Spectral Features ofm-no Complexes Synthesis ofno Complexes Reactivity ofmetal-nitrosyl Complexes Polydentate Nitrogen Donor Ligands Organometallic Porphyrin and Corrin Complexes (Written with Gang Vo) Overview Structures of Metal-Porphyrin Complexes Synthesis of Metal-Porphyrin Complexes Reactivity of Metal-Porphyrin Complexes 164

5 X CONTENTS Bis-Sulfonamide Complexes (Written with Prof. Patrick J. Walsh) Bonding in Bis-Sulfonamido Complexes Synthesis of Bis-Sulfonamide Complexes Thermodynamics of Metal-Bis-Sulfonamido Bonds Pyrazolylborate Ligands (Written with Dr. Jaclyn M. Murphy) Overview Bonding of Polypyrazolylborate Ligands Synthesis of Polypyrazolylborate Ligands and Complexes Reactions of Polypyrazolylborate Complexes $-Diketiminate Complexes Overview Structure and Bonding of P-Diketiminate Ligands Synthesis of P-Diketirnines and [3-Dikeuminate Complexes Examples of p-diketiminate Complexes Transition Metal Complexes with Anionic Oxygen Ligands (Written with Prof. Pinjing Zhao) Transition Metal-Alkoxo Complexes Overview Alkoxide Complexes of the Early Transition Metals Overview Bonding of Early-Metal Alkoxides Preparation of Early-Metal-Alkoxo Complexes Reactivity of Early-Metal-Alkoxo Complexes Early-Metal Alkoxides as Ancillary Ligands Steric and Electronic Properties Catalytic Reactions of Early-Metal-Alkoxo Complexes Alkoxide Complexes of the Late Transition Metals Overview Bonding of Late-Metal Alkoxides Thermodynamics of Late-Metal-Alkoxo Bonds Late-Metal Alkoxides as Ancillary Ligands Preparation of Late-Metal-Alkoxo Complexes Reactivity of Late-Metal-Alkoxo Complexes Catalytic Reactions oflate-metal-alkoxo Complexes Metal P-Diketonate Complexes Transition-Metal-Boryl Complexes (Written with Dr. Jaclyn M. Murphy) Overview Metal-Boryl Bonding Thermodynamics of Metal-Boryl Complexes Synthesis of Metal-Boryl Complexes Reactivity of Metal-Boryl Complexes Transition-Metal-Phosphido Complexes (Written with Prof. Jack R. Norton) Structures of Phosphido Complexes Dynamics of Phosphido Complexes Thermodynamic Properties of Phosphido Complexes Reactivity of Phosphido Complexes Transition Metal-Thiolate-Complexes (Written with Dr. Elsa Alvaro) Overview Bonding and Structures of Transition-Metal-Thiolate Complexes Thermodynamics of M-SR Bonds Synthesis of Metal-Thiolate Complexes Reactivity of Thiolate Complexes Transition-Metal-Silyl Complexes (Written with Dr. Tim A. Boebel) Overview Electronic Properties of Free and Coordinated Silyl Groups Structures of Metal-Silyl Complexes Spectral Properties of Metal-Silyl Complexes Synthesis of Metal-Silyl Complexes Stability and Reactivity of Silyl Complexes 200

6 CONTENTS XI 4.8. Halide Ligands Overview Steric and Electronic Properties Reactivity of Metal-Halide Complexes 203 References and Notes 204 Chapter 5. Ligand Substitution Reactions Introduction Overview of Ligand Substitution Definitions of Associative, Dissociative, and Interchange The Basic Factors that Control Ligand Substitution Mechanisms Scope of the Chapter Thermochemical Considerations Mechanisms of Ligand Substitutions Mechanisms of Ligand Substitutions of 16-Electron and 17-Electron Complexes Associative Substitutions of Square-Planar ds Complexes Stereochemistry of Associative Substitution and Cis-Trans Isomerization The Rate Law for Associative Substitutions Dependence of the Rates on the Incoming Ligand, the Departing Ligand, and the Metal Center Trans and Cis Effects Associative versus Dissociative Substitutions ofsquare-planar Complexes Associative Substitutions of 17-Electron Complexes Substitution Reactions of 18-Electron Complexes Dissociative Substitution Reactions General Features of the Kinetics of Dissociative Ligand Substitution Reactions ofnuco) as Quintessential Examples of Dissociative Substitutions Steric Effects on Dissociative Substitution Stereochemistry ofdissociative Substitution Substitution ofweakly Bound Ligands in 18-Electron Complexes Electronic Effect ofancillary Ligands on the Rates of Dissociative Substitution Reactions The Cis Effect S tereochemistry of Substitutions of Octahedral Compounds Substitutions of 18-Electron Complexes that Deviate from Pure Thermally Induced Dissociative Mechanisms Substitutions ofm(co)6 Complexes an Associative Term in the Rate Law 241 Occur with Catalyzed and Assisted Ligand Substitution Reactions Ligand Substitution Catalyzed by Electron Transfer Ligand Substitutions by Radical Chains Initiated by Atom Abstractions Photoinduced Dissociation of Ligands Oxidation of Coordinated CO Other Assisted Ligand Substitutions Substitution Reactions Involving Polyhapto Ligands Substitutions for Dienes and Trienes Substitutions for Arenes and Arene Exchange Reactions Associative Substitution by Pentadienyl Ligand Ring Slip Ligand Substitutions in Metal-Metal Bonded Bimetallic and Higher Nuclearity 5.7. Summary 255 References and Notes 255 Clusters 253 Chapter 6. Oxidative Addition of Nonpolar Reagents Definitions, Examples, and Trends Definition of Oxidative Addition Qualitative Trends for Oxidative Addition Thermodynamics of Oxidative Addition Oxidative Addition of Dihydrogen General Mechanism for the Oxidative Addition ofh Examples of Oxidative Addition of H2 to a Single Metal Center Oxidative Addition of H2 to Two Metal Centers Oxidative Addition of Silanes Oxidative Addition of C-H Bonds Early History of C-H Bond Oxidative Addition Intramolecular C-H Oxidative Addition Intermolecular Oxidative Addition of C-H Bonds 275

7 xii CONTENTS Selectivity of Alkane Oxidative Addition Mechanism of Oxidative Addition of C-H Bonds Examples of Complexes that Oxidatively Add Alkanes Synthetic Applications of C-H Oxidative Addition of Alkyl Groups Dinuclear Activation of 282 Hydrocarbons 6.5. Addition of H-H and C-H Bonds to Transition Metal Complexes Without Oxidation and Reduction Sigma-Bond Metathesis Involving d Complexes Potential Sigma-Bond Metatheses Involving Late Transition Metal Complexes [2 + 2] Additions Across Metal-Ligand Multiple Bonds Oxidative Addition of C-C Bonds Oxidative Addition of E-E Bonds Summary 292 References and Notes 292 Chapter 7. Oxidative Addition ol Polar Reagents Introduction Oxidative Addition by SN2 Pathways Oxidative Additions by One-Electron Mechanisms Inner-Sphere Electron Transfer and Caged Radical Pairs Radical Chain Pathways Outer-Sphere Electron-Transfer Mechanisms Atom Abstraction and Combination of the Resulting Radical with a Second Metal Concerted Oxidative Additions Concerted Oxidative Additions of Reagents with C-X Bonds of Medium Polarity Oxidative Addition of Reagents with H-X Bonds of Medium Polarity Dinuclear Oxidative Additions of Electrophilic A-B Summary 317 References and Notes Effect ofmetal Identity and Electron Density The Effect of Steric Properties The Effect of Participating Ligands The Effect of Coordination Number The Effect of Geometry The Effect of Light: Photochemically Induced Reductive Elimination Reductive Eliminations Organized by Type of Bond Formation Reductive Elimination to Form C-H Bonds Overview and Principles Examples Evidencefor Intermediate Alkane and Arene Complexes The Effect ofancillary Ligands on C-H Bond-Forming Reductive Elimination Reductive Elimination to Form X-H Bonds Reductive Elimination to Form C-C Bonds Trends and Principles The Effect of Participating Groups The Effect of Coordination Number The Effect of Bite Angle Survey of Carbon-Carbon Bond-Forming Reductive Eliminations Reductive Elimination to Form C-X Bonds Mechanisms of Reductive Eliminations to Form C-X Bonis Survey of Reductive Eliminations to Form C-X Bonds Reductive Eliminations to Form C-X Bonds from Aryl and Alkylplatinum(IV) Complexes Reductive Eliminations to Form C-X Bonds from Arylpalladium(II) Complexes Reductive Eliminations to Form C-X 8.3. Summary 345 References and Notes 345 Bonds from Acyl Complexes 344 Chapter 8. Reductive Elimination Overview Changes in Electron Count and Oxidation State Factors thataffect the Rates of Reductive Elimination 322 Chapter 9. Migratory Insertion Reactions Overview and Basic Principles Description of Migratory Elimination 349 Insertion and Changes in Geometry and Electron Count During Migratory Insertion and Elimination 350

8 CONTENTS xiii 9.2. Specific Classes of Insertions Insertions of Ligands Boundby a Single Atom Insertions of Carbon Monoxide Examples of CO Insertions into Metal-Hydrocarbyl Complexes of Examples Insertions of CO into M-X Bonds (X = N, O, and Si) Kinetics and Mechanism of CO Insertions into Metal-Alkyl Complexes Insertions into 18-Electron Complexes Insertions into 16-Electron d8 Complexes Stereochemistry at Carbon A. Stereochemistry at the Metal Structure of the Unsaturated Intermediate Solvent Effects Migratory Aptitudes of R Thermodynamic Effects on Migratory Aptitudes Kinetic Effects on Migratory Aptitudes Catalysis of CO Insertion Catalysis by Lewis Acids Redox Acceleration Insertions of Other Ligands Bound Through a Single Atom Insertions of Carbenes Insertions of Polyhapto Ligands into Metal- Ligand Covalent Bonds Insertions into Metal-Hydride Bonds Insertions of Olefins into Metal- Hydride Bonds Insertions of Alkynes into Metal- Hydride Bonds Insertion of Ketones and Imines into Metal-Hydride Bonds Insertions of Olefins into Metal-Carbon Bonds Insertions of Olefins into Metal-Hydrocarbyl a-bonds Insertions of Olefins into Metal-Acyl Bonds Insertions of Alkynes into Metal-Carbon Bonds Insertions of Polyenes into Metal-Carbon Bonds Insertions of Aldehydes and Imines into Metal-Carbon Bonds Insertions of Olefins and Acetylenes into Metal-Heteroatom Bonds Insertion of Olefins into Metal-Oxygen Bonds Insertions of Olefins into Metal-Nitrogen Bonds Insertions of Olefins and Acetylenes 9.3. Summary 389 into Metal-Silicon and Metal-Boron Bonds 388 References and Notes 390 Chapter 10. Elimination Reactions Overview of the Chapter Scope of Organometallic Elimination Chemistry B-Elimination Processes p-hydrogen Eliminations fi-hydrogen Elimination from Metal-Alkyl Complexes Effect of Conformation and Coordination Number on the Rate of B-Hydrogen Elimination Effect of Electronics on the Rate of p-hydrogen Elimination Effect of Ancillary Ligands on the Rate of p-hydrogen Elimination fi-hydrogen Elimination from Metal Alkoxides and Amides (3-Hydrogen Elimination from Metal-Silyl Complexes p-hydrocarbyl Eliminations p-altyl Eliminations from Alkyl Complexes fi-alkyl and j3-aryl Eliminationsfrom Alkoxido and Amido Complexes /3-Halide and Alkoxide Elimination a-hydrogen Eliminations and Abstractions Summary 413 References and Notes 414 Chapter 11. Nucleophilic Attack on Coordinated Ligands Fundamental Principles Nucleophilic Attack on Transition Metal Com plexes of Carbon Monoxide and Isonitriles 419

9 xiv CONTENTS General Trends Examples of Nucleophilic Monoxide and Isonitriles 420 Attack on Carbon Nucleophilic Attack On Carbene and Carbyne Complexes Nucleophilic Cleavage cr-bonds 422 of Metal-Carbon General Principles and Trends Examples of Nucleophilic Attack on cr-bound Ligands Nucleophilic Attack on ^-Unsaturated Hydrocarbon Ligands General Trends Nucleophilic Attack on -rf-olefin Complexes Overview of Nucleophilic Attack on rf-olefin Complexes Specific Examples of Nucleophilic Attack on if'-olefin Complexes: Reactions of[cpfeu(co)2]\ [CpPd"Lr and Square Planar M" (M=Pd, Pt) Olefin Complexes Nucleophilic Attack on Square Planar Pd(II) Diene and Allene Complexes Nucleophilic Attack on Ti2-Alkyne Complexes Reactions of T^-Arene Complexes Nucleophilic Attack on Imine and Aldehyde Complexes Nucleophilic Attack on Polyhapto (tq3 Ligands Nucleophilic Attack on in3-allyl Complexes Nucleophilic Attack on if-diene Complexes Nucleophilic Attack on irf-dienyl Complexes Nucleophilic Attack on T 6-Arene and Cycloheptatrienyl Complexes Overview of Nucleophilic Attack on rf-arene Complexes Examples of Nucleophilic Attack on TT-Arene Summary 446 Complexes 444 References and Notes 447 Chapter 12. Electrophilic Attack on Coordinated Ligands Overview and Basic Principles Electrophilic Cleavage of Metal-Carbon and Metal-Hydride a-bonds Scope of Electrophilic Cleavage of Metal- Carbon and Metal-Hydride Mechanism of Electrophilic Attack 457 cr-bonds Mechanism of Attack of Main Group Electrophiles on Alkyl Complexes Possessing d-electrons Mechanism ofprotonolysis ofmetal-carbon Bonds in Complexes Possessing d-electrons Mechanism ofprotonation of Metal-Hydride Bonds in Complexes Containing d-electrons Mechanism of Electrophilic Attack on Alkyl Complexes that Lack d-electrons Electrophilic Insertion Reactions: Sulfur Dioxide, Carbon Dioxide and Related Electrophiles Electrophilic Modification of Coordinated Ligands Attack at the a-position Attack at the a-position of an Alkyl Group Electrophilic Attack on Carbene and Carbyne Complexes Attack at the (3-Position Attack at the ^-Position Attack on Coordinated Olefins and Polyenes Attack of Carbonyl Compounds and Protons on Olefin Complexes Hydride Abstraction by Electrophilic Attack on Diene Complexes Electrophilic Attack on it-polyenyl Complexes Electrophilic Attack on tf-arene and Heteroarene Complexes Summary 476 References and Notes 477 Chapter 13. Metal-Ligand Multiple Bonds Introduction to Metal-Ligand Multiple Bonds Carbene Complexes Classes of Carbene Complexes Origin of the Electronic Properties and Schrock Carbenes 483 of Fischer

10 CONTENTS XV Synthesis of Carbene Complexes Synthesis of Fischer Carbene Complexes Synthesis of Vinylidene Complexes Synthesis ofsome Classic Alkylidene Complexes Synthesis of the First Schrock Carbene Complexes Synthesis of the Schrock Alkylidene Catalysts Synthesis of Tebbe's Reagent Synthesis of Af-Heterocyclic Carbene Complexes Reactivity of Carbene Complexes Reactivity of Fischer Carbene Complexes Reactions with Nucleophiles Conversion to Carbyne Complexes Reactions Related to Those of Enolates Cyclopropanations Annulations: The Dotz Reaction Reactivity of Vinylidene Complexes Reactivity of Alkylidene and Alkylidyne Complexes Examples of [2+2] Reactions of Alkylidenes and Alkylidynes Fomal [2+2] Reactions with C-H CT-Bonds Silylene Complexes Overview of Silylene Complexes Bonding of Silylene Complexes Examples of Isolated Silylene Complexes Reactivity of Silylene Complexes Metal-Heteroatom Multiple Bonds Scope of the Section Overview Bonding of Oxo and Imido Complexes Synthesis Complexes 512 of Metal-Imido and Metal-Oxo Synthesis ofmetal-imido Complexes Synthesis of Metal-Oxo Complexes Reactions of Imido and Oxo Compounds [2+2] and [3+2] Cxjcloadditions Atom Transfer of Oxo and Imido Groups to Olefins Reactions with C-H Bonds Reactions with Electrophiles Migrations ofalkyl and Hydride Groups from MtoOorN Catalytic Reactions of Imido and Metal-Oxo Compounds Through Organometallic Intermediates Nitrido Ligands (Written Rosenfeld) Overview 527 with Dr. Devon C Bonding ofnitrido Ligands Structural and Spectral Features Synthesis ofmetal-nitrido Complexes Reactions of Metal-Nitrido Complexes 529 References and Notes 530 Chapter 14. Principles of Catalysis (Written with Prof. Patrick J.Walsh) General Principles Definition of a Catalyst Energetics of Catalysis Reaction Coordinate Diagrams of Catalytic Reactions Origins of Transition State Stabilization Terminology of Catalysis The Catalytic Cycle Catalyst Precursors, Catalyst Deactivation, and Promoters Quantification ofefficiency Kinetics of Catalytic Reactions and Resting States Homogeneous vs. Heterogeneous Catalysis Distinguishing Homogeneous from Heterogeneous Catalysts Fundamentals of Asymmetric Catalysis Importance of Asymmetric Catalysis Classes of Asymmetric Transformations Nomenclature Description ofstereoselectivity The Origin of Stereoselection Energetics of Stereoselectivity Reaction Coordinates of Catalytic Enantioselective Reactions Reactions with a Single Enantioselectivity-Determining Step 554

11 xvi CONTENTS Reactions with Reversiblity Prior to the Enantioselectivity-Deterrruning Step: The Curtin-Harnrriett Principle Applied to Asymmetric Catalysis Theory Two Examples ofreactions Under Curtin-Hammett Conditions Asymmetric Hydrogenation Asymmetric Allylic Alkylation Transmission of Asymmetry Effect of C2 Symmetry Quadrant Diagrams Structures ofligands Generating Highly Selective Catalysts ("Privileged Ligands") Alternative Asymmetric Processes: Kinetic Resolutions and Desymmetrizations Kinetic Resolutions Quantification of Selectivity in Kinetic Resolutions Energetics of Selectivity in Kinetic Resolutions Examples of Kinetic Resolutions Dynamic Kinetic Resolution Example of Dynamic Kinetic Resolutions: Dynamic Kinetic Resolution of 1,3-Dicarbonyl Compounds Through Asymmetric Hydrogenation Dynamic Kinetic Asymmetric Transformations Desymmetrization Reactions Two Examples of Summary 571 Desymmetrization Desymmetrization ofachiral Dienes via Catalytic Asymmetric Hydrosilylation Desymmetrization Catalyzed References and Notes 571 via the Palladium- Heck Reaction 570 Chapter 15. Homogeneous Hydrogenation Introduction A Perspective on the Homogeneous Catalytic Hydrogenation of Olefins Selected Examples of Achiral Homogeneous Hydrogenation Catalysts Rhodium Catalysts for Olefin Hydrogenation Neutral Rhodium Catalysts Preparation of Wilkinson's Catalyst The Reactivity Catalyst 579 of Wilkinson's Cationic Rhodium Catalysts Iridium Catalysts: Crabtree's Catalyst Ruthenium Catalysts for Olefin Hydrogenation Lanthanide Catalysts Directed Hydrogenation Mechanisms of Homogeneous Olefin and Ketone Hydrogenation Background Overview of the Typical Mechanisms Mechanisms Occurring by Insertions of Olefins into Dihydride Complexes Hydrogenation by Wilkinson's Catalyst Mechanism of the Oxidative Addition Step Mechanism of the Migratory Insertion Step Hydrogenation by Cationic Rhodium Catalysts Cationic Rhodium Complexes Containing Aromatic Phosphines Cationic Rhodium Catalysts Containing Alkylphosphines Cationic Iridium Catalysts Containing Alkylphosphines Catalysts that React by Insertions of Olefins into Monohydride Intermediates Hydrogenation by Rhodium Carbonyl Hydride Catalysts Hydrogenation by Ruthenium Catalysts Mechanism ofhydrogenation by Ru(PPh3)3H(Cl) Mechanism of Hydrogenation of Olefins and Ketones by RuL2(k2- OAc)2 and [RuL2Cy2 597

12 CONTENTS XVII Monohydride Catalysts Reacting Through Radical Pathways d -Monohydride Catalysts Reacting Through a-bond Metathesis Pathways Outer-Sphere Mechanism for the Hydrogenation ofketones and hnines Ionic Hydrogenations Ligands Used for Asymmetric Hydrogenation Aromatic Bisphosphines Aromatic Bisphosphines Containing Backbone Chirality Ligands Containing Axial Chiral Backbones Compounds Containing Chiral Ferrocenyl Backbones Ligands Containing Aliphatic Backbones Aliphatic Bisphosphines P-Chiral Phosphines P,N Ligands Phosphites and Phosphoramidites Examples of Asymmetric Hydrogenation and Transfer Hydrogenation Classes of Asymmetric Hydrogenations of Olefins Asymmetric Hydrogenation of Enamides Asymmetric Hydrogenation of Dehydro a-amino Acids [a-(acylamino)acrylic Acids and Esters] Asymmetric Hydrogenation of Dehydro (3-Amino Acids [p-(acylamino)acrylic Acids and Esters] Asymmetric Hydrogenation of Simple Enamides Asymmetric Hydrogenation of a-(acyloxy)- acrylates Asymmetric Hydrogenation ofacrylic Acids Asymmetric Hydrogenation of Unsaturated Alcohols Asymmetric Hydrogenation of Unfunctionalized Olefins Asymmetric Hydrogenation of Ketones Asymmetric Hydrogenations of Functionalized Ketones Asymmetric Hydrogenations of a-keto Esters Asymmetric Hydrogenation of (3-Keto Esters Asymmetric Hydrogenations of fi-diketones Asymmetric Hydrogenations of a- and /3-Amino and Hydroxy Ketones Hydrogenation Ketones 626 of Unfunctionalized Asymmetric Hydrogenation of Imines Asymmetric Hydrogenation of Cyclic Imines Asymmetric Hydrogenation of Acyclic N-Alkyl Imines Asymmetric Hydrogenation of Acyclic N-Aryl Imines Asymmetric Hydrogenation of Aroylhydrazones and Phosphinylketimines Asymmetric Transfer Hydrogenation of Ketones and Imines Mechanism of Asymmetric Catalytic Hydrogenation Esters 636 of a-acetamidocinnamic Acid Hydrogenation of Alkynes and Conjugated Dienes Rhodium-Catalyzed Hydrogenation of Alkynes and Conjugated Dienes Chromium-Catalyzed Hydrogenation of Alkynes and Conjugated Dienes Palladium-Catalyzed Hydrogenation of Alkynes and Conjugated Dienes Homogeneous Catalytic Hydrogenation and Heteroarenes 644 of Arenes Homogeneous Catalytic Hydrogenation of Polycyclic Arenes Hydrogenation of Monocyclic Arenes Asymmetric Hydrogenation of Heteroarenes Asymmetric Hydrogenation ofsix-membered Ring Heteroarenes Asymmetric Hydrogenation offive- Membered Ring Heteroarenes 649

13 xviii CONTENTS Homogeneous Hydrogenation of Other Functional Groups (Written with Prof. Jing Zhao) Hydrogenation of Esters Hydrogenation of Carboxylic Anhydrides and Imides Hydrogenation of Nitriles Summary 656 References and Notes 657 Chapter 16. Hydrofunctionalization and Oxidative Functionalization of Olefins Introduction and Scope Homogeneous Catalytic Hydrocyanation of Olefins and Alkynes Introduction to Hydrocyanation Examples of Alkene Hydrocyanation Mechanism of Hydrocyanation Mechanism of the Hydrocyanation of Alkenes ,2. Mechanism of Deactivation Hydrocyanation of Dienes Asymmetric Hydrocyanation Hydrocyanation of Alkynes Summary of Catalytic Hydrocyanation Hydrosilylation and Disilylation Introduction to Hydrosilylation and Disilylation Purpose for Hydrosilylation History and Types of Catalyst Examples of Hydrosilylations Hydrosilylation of Olefins with Achiral Catalysts Hydrosilylation of Vinylarenes Hydrosilylation of Dienes Dehydrogenase Silylation of Olefins Hydrosilylation of Alkynes Asymmetric Hydrosilylation of Olefins Hydrosilylation of Ketones and lmines Mechanism of Hydrosilylation Induction Periods and Phase of the Reactions Catalyzed by Speier's and Karstedt's Catalysts Overall Catalytic Cycles The Chalk-Harrod Mechanism Evidence for a Modified Chalk- Harrod Mechanism Alkene Hydrosilylation by cr-bond Metathesis Mechanism of Alkyne Disilation 690 Hydrosilylation Transition-Metal-Catalyzed Hydroboration, Diboration, Silylboration, and Stannylboration Overview of Hydroboration and Diboration History of Catalytic Hydroboration Examples of Metal-Catalyzed Hydroboration Asymmetric Hydroboration Mechanism of the Hydroboration of Olefins Diboration, Silylboration, and Stannylboration Diboration, Silylboration, and Stannylboration ofalkynes Diboration of Alkenes Mechanism of Diborations Transition-Metal-Catalyzed Hydroamination of Olefins and Alkynes Introduction and Fundamentals of Hydroamination Scope of Hydroamination Hydroamination ofalkenes Hydroamination of Vinylarenes Hydroamination ofallenes Hydroamination of 1,3-Dienes Hydroamination ofalkynes Hydroamination of Alkynes Catalyzed by Group 4 Metal Complexes Hydroamination of Alkynes Catalyzed by Lanthanide and Actinide Complexes Hydroamination of Alkynes Catalyzed by Rhodium and Palladium Complexes Mechanisms of Transition-Metal-Catalyzed Hydroamination Overview of the Mechanisms of Transition- Metal-Catalyzed Hydroaminations 712

14 CONTENTS Xix Hydroamination by Attack ofamines on ir-complexes Hydroamination by Attack on TT-Olefin and Alkyne Complexes Hydroamination by Attack of Amines on it-auyl and ir-benzyl Complexes Hydroamination by Attack of Amines on ir-arene Complexes Hydroamination by Insertions of Olefins into Metal Amides Hydroamination by [2+2] Cycloadditions Oxidative Fimctionalization of Olefins Overview The Wacker Process Description of the Process Mechanism of the Wacker Process (Written with Prof. Jack R. Norton) Olefin Oxidations Related to the Wacker Process Intermolecular Additions of Alcohols and Carboxylates Intramolecular Additions of Alcohols and Carboxylates Wacker-Type Oxidations in Natural Products Synthesis Oxidative Aminations of Olefins Intermolecular Oxidative Aminations Intramolecular Oxidative Animation Palladium-Catalyzed Difunctionalizations of Olefins Mechanistic Studies on Wacker Oxidations with Alcohol, Phenol, and Amide Nucleophiles Overview Mechanism of C-X Bond Formation Mechanism ofreoxidation Summary 735 References and Notes 735 Chapter 17. Catalytic Carbonylation Overview Catalytic Carbonylation to form Acetic Acid and Acetic Anhydride (Written with Prof. Charles P. Casey) Rhodium-Catalyzed Carbonylation of Methanol: Monsanto's Acetic Acid Process Carbonylation of Methyl Acetate: Eastman Chemical's Acetic Anhydride Process Iridium-Catalyzed Carbonylation of Methanol: BP'S Cativa Process Hydroformylation of Olefins (Written with Prof. Charles P. Casey) Overview Hydroformylation Catalyzed by HCo(CO) Mechanism ofhydroformylation Catalyzed byhco(co) Regioselectivity ofhydroformylation Catalyzed by HCo(CO) Hydroformylation Catalyzed by HCo(CO)3(PR3) Comparison of Rate, Selectivity, and Mechanism to Hydroformylation Catalyzed byhco(co)i Hydroformylation of'internal Alkenes Catalyzed by HCo(CO)3(PR3) Rhodium-Catalyzed Hydroformylation Overview Rhodium Catalysts for Hydroformylation Containing Triarylphosphine Ligands Discovery and Reactivity of the Original Catalyst Mechanism of Hydroformylation Catalyzed by HRh(CO)2(PPh3) Water-Soluble Rhodium Hydroformylation Catalysts Rhodium Catalysts Containing Chelating Diphosphine Ligands Early Studies with Less Selective Catalysts Catalysts Containing Wide-Bite- Angle Bisphosphines Effect of Diphosphine Electronic Properties on Regioselectivity Rhodium-Catalyzed Hydroformylation of Internal Alkenes Hydroformylation Catalyzed by Rhodium Complexes ofphosphites Rhodium-Catalyzed Hydroformylation of Functionalized Alkenes Enantioselective Hydroformylation 765

15 XX CONTENTS Hydroaminomethylation History and Overview of Recent Developments Scope of Hydroaminomethylation Mechanism of Hydroaminomethylation Hydrocarboxylation and Hydroesterification of Alkenes and Alkynes Overview Synthetic Targets for Hydroesterification and Hydrocarboxylation Catalysts for the Hydi-oesterification and Hydrocarboxylation of Olefins and Alkynes Scope of Hydroesterification and Hydrocarboxylation Hydroesterification and Hydrocarboxylation of Alkenes Intermolecular Hydroesterification and Hydrocarboxylation of Alkenes Intramolecular Hydroesterification of Olefins Hydroesterification ofalkynes Hydroesterification ofbutadiene Mechanism of Hydroesterification Carbonylation of Epoxides and Aziridines (Written with Prof. Geoffrey W. Coates) Ring-Expansion Carbonylation of Epoxides and Aziridines Overview History of Epoxide and Aziridine Carbonylation Types of Catalysts and Scope of Substrates for Epoxide Carbonylation Carbonylation of Lactones and Epoxides to Succinic Anhydrides Ring-Opening Epoxide Carbonylation Types of Catalysts and Scope of Substrates for Aziridine Carbonylation Mechanism of Epoxide Carbonylation Carbonylations of Organic Halides Carbonylations of Organic Halides to form Esters and Amides Discovery and Scope Mechanism ofaryl Halide Esterification and Antidation Copolymerization of CO and Olefins Overview of the Process and Polymer Properties Development of Catalysts for the Synthesis of CO/Ethylene Copolymerization Mechanism of the Coplymerization of CO and Ethylene Overall Cycle: The Steps ofchain Propagation Chain Termination and Catalyst Decomposition A. Copolymerization of CO and a-olefins Overview ofthe Copolymerization of CO and a-olefins Copolymerization of Carbon Monoxide and Styrene Overall Mechanism Control of Stereochemistry Copolymerization ofcarbon Monoxide and Propene Regiochemistry of Insertion Stereochemistry of Insertion Polymer Structure from the Copolymerization Propene 808 of CO and Pauson-Khand Reactions (Written with Dr. Qilong Shen) Overview Origin of the Pauson-Khand Reaction Effects of Additives Catalysts Other Than Co2(CO) Pauson-Khand Reactions with Allenes Catalytic Asymmetric Pauson-Khand Reactions Intermolecular Pauson-Khand Reaction Applications of the PKR Mechanism of the Pauson-Khand Reaction 814 References and Notes 816 Chapter 18. Catalytic C-H Functionalization Overview Platinum-Catalyzed Alkane and Arene Oxidations via Organometallic Intermediates Early Platinum-Catalyzed Processes 827 C-H Activation More Practical Platinum Catalysts for Alkane Functionalization Mechanism of the Pt-Catalyzed Oxidations 829

16 CONTENTS xxi Directed Oxidations, Animations, and Halogenations of Alkanes and Arenes Carbonylation of Arenes and Alkanes Oxidative Carbonylation ofalkanes and Arenes Alkylative Carbonylation Arenes 837 of Alkanes and Direct Carbonylation to Aldehydes Dehydrogenation Early Studies Dehydrogenation Catalyzed by Complexes of Pincer Ligands Alkane Metathesis via Dehydrogenation Mechanism of Dehydrogenation Hydroarylation Directed Hydroarylation of Olefins Overview Reaction Scope and Catalysts Mechanisms of Directed Hydroarylation of Olefins Directed Hydroarylation of Alkynes Undirected Hydroarylation and Oxidative Arylation of Olefins Functionalization of Alkanes and Arenes with Main Group Reagents Borylation of Alkanes Borylation of Arenes Borylation of Polyolefins Mechanism of the Alkane and Arene Borylation Silylation of Aromatic and Aliphatic C-H Bonds Hydroacylation Overview Intermolecular Hydroacylation Intramolecular Hydroacylation Mechanism of Hydroacylation Directed Intermolecular Hydroacylation Functionalization of C-H Bonds by Carbene Insertions Overview Intramolecular C-H Functionalization by Carbene Insertion Intermolecular C-H Functionalization by Carbene Insertion H/D Exchange 869 References and Notes 870 Chapter 19. Transition Metal-Catalyzed Coupling Reactions Overview of Cross-Coupling The Classes of C-C Bond-Forming Coupling Reactions Early Studies on Cross-Coupling: Coupling with Organomagnesium Reagents Coupling of Organozinc Reagents Coupling of Organotin Reagents Coupling of Organosilicon Reagents Coupling of Organoboron Reagents Coupling of Alkynes Coupling Reagents 881 of Enolates and Related Coupling at Aliphatic Electrophiles Coupling of Olefins Coupling of Cyanide Enantioselective Cross Coupling The Mechanisms of Cross Coupling Mechanism of the Overall Catalytic Processes Mechanism of Palladium-Catalyzed Cross Coupling with Main Group Organometallic Nucleophiles Mechanism of Homocoupling Mechanism of the Olefination ofaryl Halides (Mizoroki-Heck Reaction) Mechanism of the Individual Steps of the Cross-Coupling Process The Oxidative Addition Step Mechanism oftransmetallation Mechanism ofreductive Elimination Effects of Catalyst Structure on Cross Coupling Effect of Chelation Effect of Steric Properties Effect ofligand Electronic Properties Applications of C-C Cross Coupling Cross-Coupling Reactions that Form Carbon- Heteroatom Bonds Overview Coupling of Aryl Halides with Amines Scope of the Reaction Catalysts for C-N Coupling Mechanism of the C-N Coupling 911

17 XXII CONTENTS Carbonylative Coupling Carbonylation of Organic Ketones 914 Processes 914 Halides to Form Mechanism of Carbonylative Coupling to form Ketones Formylation of Organic Halides Copper-Mediated Cross-Coupling Reactions (Written with Dr. Shashank Shekhar) Copper-Mediated Cross Coupling to Form C{aryl)-N, C(aryl)-0 and C(aryl)-S Bonds Classes of Copper Catalysts for Carbon-Heteroatom Bond-Forming Coupling Reactions Copper-Catalyzed Carbon-Nitrogen Cross-Coupling Reactions Copper-Catalyzed Coupling of Amines Copper-Catalyzed Coupling of Arylamines Copper-Catalyzed Coupling of Alkylamines Copper-Catalyzed Coupling of Amides with Aryl Halides Copper-Catalyzed Reactions of Aryl Halides with Heterocyclic Amines Copper-Catalyzed Coupling of Aryl Halides with Alcohols and Thiols Reactions of Aryl Phenols 926 Halides with Reactions of Aryl Halides with Aliphatic Alcohols Reactions of Aryl Halides with Amino Alcohols Copper-Catalyzed Reactions of Aryl Halides with Thiols Mechanism of Copper-Catalyzed Coupling of Aryl Halides with Amines, Alcohols, and Thiols Reactions of Aryl Boronic Acids with Amines and Alcohols (Chan-Evans-Lam Couplings) Copper-Catalyzed Cross Coupling C-C Bonds Cross Coupling to Form C(Alkyl)-C Bonds with Copper 933 to Form C(sp3)-C(sp3) Coupling Mediated by Copper Reagents Copper-Catalyzed C(sp3)-C(sp3) Coupling Copper-Catalyzed Cross Coupling Aromatic C-C Bonds Coupling of fi-diketones, to Form Cyanoesters, and Malonates Copper-Catalyzed Couplings 937 Stille and Suzuki Direct Arylation (Written with Dr. Mark E. Scott, Dr. Dino Alberico, and Prof. Mark Lautens) Introduction and Overview Mechanisms of Direct Arylations Transition Metal Catalysts Arylation 939 for Direct Regioselectivity of Direct Arylations General Comments on Reaction Conditions for Direct Arylation Catalytic Direct Oxidative Cross Couplings (Written with Dr. Mark E. Scott, Dr. Dino Alberico, and Prof. Mark Lautens) Summary 950 References and Notes 951 Chapter 20. Allylic Substitution Overview Early Developments Toward Enantioselective Allylic Substitution Stoichiometric Attack on Palladium Allyl Complexes The First Catalytic Allylic The First Catalysts for Allylic Substitutions 968 Substitutions Substrate Scope and Catalysts Scope of Electrophile Scope of Nucleophile Metals Used for Allylic Substitutions Mechanism of Allylic Substitution Mechanism of Palladium-Catalyzed Reactions Mechanism of Reactions Catalyzed by Complexes Other Than Palladium Regioselectivity of Allylic Substitutions Trends and Origins of Regioselectivity of Palladium-Catalyzed Reactions Reactions of Carbon Nucleophiles Reactions of Heteroatom Nucleophiles 981