Applied Homogeneous Catalysis

FOREWORD
PREFACE
PART I CHEMICAL BASICS
DEFINITION, OPTIONS, AND EXAMPLES: WHAT ACTUALLY IS CATALYSIS?
Definition of Catalysis
The Different Varieties of Catalysis
The 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 Separation
Reactions 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 Processes
Asymmetric 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 TRENDS
TANDEM 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 Reactions
New Catalysts
New Methods

ANSWERS TO THE QUICKIES

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 Dortmund
University, 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 Universität 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.

A. Behr, Universität Dortmund, Lehrstuhl für Technische Chemie, Dortmund; P. Neubert, Technische Universität Dortmund, Germany