Applied Homogeneous Catalysis

Arno Behr was born in 1952 in Aachen, Germany. He received his Diploma in chemistry from RWTH Aachen University and fi nished his PhD in 1979 under supervision of Prof. Willi Keim. After being employed at Henkel KGaA he is a full Professor of Technical Chemistry at DortmundUniversity, Germany since 1996. Since 35 years his research interests cover homogeneous transition-metal catalysis, conversion of petrochemicals and renewables and catalyst recycling. During the last 30 years he became an experienced lecturer, held GDCh- and Dechema lectures and was involved in several advanced master and PhD courses. Peter Neubert was born in 1981 in Castrop-Rauxel, Germany. He studied chemistry at Technische Universitat Dortmund, Germany and Bergen University, Norway. He received his diploma in 2009 under the supervision of Professor Arno Behr. He is currently a doctoral candidate in the same group. His current research deals with the catalytic conversion of C5 materials and the development of recycling concepts in homogeneous catalysis.

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• FOREWORD PREFACE PART I CHEMICAL BASICS DEFINITION, OPTIONS, AND EXAMPLES: WHAT ACTUALLY IS CATALYSIS? Definition of Catalysis The Different Varieties of CatalysisThe Directing Effect of the Catalyst Catalysis as a Part of "Green Chemistry"Sources of Information about Catalysis A BRIEF HISTORY: HOMOGENEOUS TRANSITION METAL CATALYSIS: A YOUNG SCIENCE A Brief History INDUSTRIAL HOMOGENEOUS CATALYSIS: WHAT IS THE ECONOMIC IMPORTANCE? Application Areas of Catalysis Important Homogeneous Catalyzed Processes Synthesis of Fine Chemicals by Homogeneous Catalysis DEFINITIONS OF IMPORTANT TERMS: SELECTIVITY, STY, TON, TOF, AND MORE. . . Conversion Yield Selectivity Other Important Target Values The Choice is Yours! BONDS, ELEMENTAL STEPS, AND CATALYST CYCLES: BASICS OF ORGANOMETALLIC CHEMISTRY Ligands Change in Oxidation State Changing of Coordination Number (CN) and Coordination Geometry The Elementary Steps Catalytic Cycles TRANSITION METAL COMPLEXES: THE "CAPTAINS" OF HOMOGENEOUS CATALYSIS Group IIIB Metals and Lanthanides Metals of Group IVB Metals of Groups VB to VIIB The "Iron Metals" of Group VIII The Noble Metals from Group VIII Gold: A Noble Metal from Group IB The Cost of Catalyst Metals The Availability of Transition Metal Catalysts A Typical Experiment: Synthesis of Pd(acac)2 THE COMPLEX LIGANDS: THE "MATES" OF HOMOGENEOUS CATALYSIS Monodentate Ligand or Chelate? Basicity of Ligands Cone Angle ("Tolman Cone Angle") The Bite Angle Costs and Accessibility of Ligands A Typical Experiment: The Synthesis of Biphephos Stability of Ligands THE SOLVENTS: THE REACTION MEDIUM Criteria for Choosing Solvents Miscibility of Solvents Solvents as Activators Solvents as Deactivators Availability and Purity of Solvents Special Solvents ASYMMETRIC CATALYSIS: THE "SPECIAL CASE"A Glossary of Asymmetric Catalysis A Quick Look Back Mechanistic Considerations Chiral Ligands Overview on Homogeneous Catalyzed Asymmetric Syntheses Industrial Applications THERMODYNAMICS OF HOMOGENEOUS CATALYSIS: WHEN DOES A CHEMICAL REACTION RUN? Gibbs Energy and Energy Plot Calculation or Assessment of the Free Reaction Enthalpy Thermodynamic Analysis of Complex Reaction Systems KINETICS OF HOMOGENEOUS CATALYSIS: HOW DOES THE REACTION PROCEED? Frequently Occurring Kinetics The Energy Diagram for Explaining Regioselectivity The Energy Diagram for Explaining Enantioselectivity Execution of Kinetic Measurements A Concrete Example: The (Isomerizing) Hydroformylation of Octenes Possible Failures in Kinetic Measurements OVERVIEW ON SPECTROSCOPIC METHODS: CAN WE SEE INTO HOMOGENEOUS CATALYSIS? UV/Visible Spectroscopy IR Spectroscopy NMR Spectroscopy Mass Spectroscopy Extended X-Ray Absorption Fine Structure Analysis Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) PART II PROCESS ENGINEERING FUNDAMENTALS REACTOR TYPES: WHERE DOES CATALYSIS OCCUR? Reactions in Homogeneous Liquid Phase Fluid-Fluid Systems The "Embarras de Richesses"Pressure Reactors New Trends OVERVIEW ON CATALYST RECYCLING METHODS: IS MY CATALYST ECONOMICAL? The Principles of Separation Precipitation Crystallization Adsorption THERMAL SEPARATION: THE SIMPLEST REMOVAL OF VOLATILE PRODUCTS The Basics Example: Hydroformylation Example: Oxidation of Ethene to Acetaldehyde Example: Carbonylation of Methanol to Acetic Acid IMMOBILIZATION ON SOLID SUPPORTS: FROM HOMOGENEOUS TO HETEROGENEOUS The Basic Principle Organic Supports Inorganic Supports LIQUID-LIQUID MULTIPHASE SYSTEMS: THE SMART APPROACH TO CATALYST SEPARATION Variants of Liquid?Liquid Biphasic (LLB) Systems Reaction and SeparationReactions with In-Situ Extraction Reactions with Post Extraction THERMOMORPHIC SOLVENT SYSTEMS: CLEVER ENHANCEMENTS Thermoregulated Phase-Transfer Catalysis Thermoregulated Microemulsions Thermoregulated Fluorous Solvent Systems Thermoregulated Polymer-Bound Catalysts Thermomorphic Multicomponent Solvent Systems A Retrospective Look at Catalyst Recycling Methods PART III HOMOGENEOUS CATALYZED REACTION TYPES AN OVERVIEW OF C?C-BONDING REACTIONS: A GUIDE THROUGH THE JUNGLE HYDROFORMYLATIONS: THE INDUSTRIAL ROUTE TO ALDEHYDES AND ALCOHOLS Substrates Catalysts Mechanisms Industrial ProcessesAsymmetric Hydroformylation A Typical Experiment: Hydroformylation of 1-Octene CARBONYLATIONS: THE VERSATILE INSERTIONS OF CARBON MONOXIDE Reactions between CO and Hydrogen Reactions of CO with Alkenes and Vinyl Arenes Reactions of CO with Dienes Reactions of CO with Alkynes Reactions of CO with Alcohols A Typical Experiment OLIGOMERIZATION AND CYCLOOLIGOMERIZATION: THE CONVERSION OF UNSATURATED ALIPHATICS INTO SHORT CHAINS OR MEDIUM-SIZED RINGS Oligomerization of Alkenes Dienes Alkynes Cooligomerizations A Typical Experiment METATHESIS: A "CHANGE-YOUR-PARTNERS" DANCE Mechanism and Catalysts Industrial Applications A Typical Experiment: Self Metathesis of 1-Octene POLYMERIZATIONS: THE PURPOSEFUL ASSEMBLY OF MACROMOLECULES Polyethylene and Ziegler Catalysts Polypropylene and Metallocene Catalysis Further Polyolefins Polydienes Polyketones Polyalkynes Post-Metallocenes Current Topics in Polymer Research A Typical Experiment TELOMERIZATIONS: THE CONSTRUCTION OF C8 AND C10 CHAINS Reactions, Mechanisms, and Catalysts Butadiene Telomerizations Telomerizations with Isoprene Telomerizations in Liquid?Liquid Biphasic Systems A Typical Experiment REACTIONS WITH CARBON DIOXIDE: THE ACTIVATION OF AN "INACTIVE" MOLECULE Carbon Dioxide and Alkanes Carbon Dioxide and Alkenes Carbon Dioxide and Dienes Carbon Dioxide and Alkynes Carbon Dioxide and Aromatics Carbon Dioxide and Hydrogen Carbon Dioxide and Epoxides Carbon Dioxide and Amines Carbon Dioxide-Containing Polymers A Typical Experiment CARBON-CARBON COUPLING WITH AROMATICS: NEW NAME REACTIONS Mizoroki-Heck Reactions Sonogashira-Hagihara Reactions Suzuki-Miyaura Reaction Cross-Couplings with Metal Organyles A Typical Experiment HYDROGENATIONS: C-H BOND FORMATION Catalysts and Mechanisms Asymmetric Hydrogenation Hydrogenation of Various Functional Groups Technical Applications A Typical Experiment OXIDATIONS: FORMATION OF C-O BONDS Wacker Oxidations Epoxidations Asymmetric Dihydroxylations Oxidative Cleavage of C=C Double Bonds Oxidations of Alkyl Aromatics A Typical Experiment AMINATIONS: FORMATION OF C-N BONDS Amination of Aryl Halides Hydroamination of Alkenes Hydroaminations of Dienes Hydroamination of Alkynes Amination of Functional Groups . . .Some More Aminations A Typical Experiment ISOMERIZATIONS: MIGRATION OF DOUBLE BONDS AND REARRANGEMENT OF THE CARBON BACKBONE Isomerization of Alkenes Isomerization of Substituted Alkenes Rearrangement of the Backbone A Typical Experiment PART IV NEW TRENDSTANDEM REACTIONS: MULTIPLE SYNTHESIS STEPS IN ONE POT Multicomponent Reactions Multifunctional Catalysis Tandem and Related Reactions A Typical Experiment COMBINATORIAL CHEMISTRY AND HIGH-THROUGHPUT CATALYST SCREENING: THE FAST WAY TO OPTIMUM RESULTS Basics and Definitions Parallel Reactor Systems Sequential Reactor Systems GREEN SOLVENTS: WORKING WITH ECO-FRIENDLY SOLVENTS Ionic Liquids Supercritical Fluids Fluorous Solvents Polyethers Conclusions ALKANE ACTIVATIONS: ACQUISITIONS OF NEW FEEDSTOCKS Mechanistic Considerations Alkane Oxidations Alkane Carbonylations Alkane Metathesis Alkane Hydrogenolysis Alkane Borylation Alkane Sulfonation A Look Back MORE EFFICIENT LIGANDS: THE BEST IS THE ENEMY OF THE GOOD Nitrogen-Containing Ligands Unusual Phosphorus Ligands Ligands Containing Elements from Group VIA Ligands Containing Elements from Group IVA NANOCATALYSIS: BETWEEN HOMOGENEOUS AND HETEROGENEOUS CATALYSIS Synthesis and Properties of Nanocatalysts Stabilization of Nanoparticles Heterogenization of Nanoparticles on Solid Supports Catalysis Involving Metal Nanoparticles HOMOGENEOUS CATALYSIS WITH RENEWABLES: USING NATURE.S TREASURES Catalytic Conversion of Fatty Compounds Catalytic Reactions of Carbohydrates Catalytic Reactions of Terpenes ELECTROCATALYSIS/SONOCATALYSIS/PHOTOCATALYSIS/MICROWAVE/EXTREME PRESSURE: ALTERNATIVE METHODS OF ACTIVATION Electrocatalysis Photocatalysis Sonocatalysis Microwave Catalysis Extreme High-Pressure Catalysis PROCESS DEVELOPMENT IN MINIPLANTS: FROM LABORATORY TO PRODUCTION Miniplant with Continuously Stirred-Tank Reactor (Miniplant I) Miniplant with Loop Reactor and Phase Separator (Miniplant II) Miniplant with Jetloop Reactor and Phase Separator (Miniplant III) Miniplant with a Mixer?Settler Battery (Miniplant IV) THE FUTURE OF HOMOGENEOUS CATALYSIS: A LOOK AHEAD New Resources New ReactionsNew Catalysts New Methods ANSWERS TO THE QUICKIES