Computational Methods in Organometallic Catalysis

Discover recent advances in the mechanistic study of organometallic catalysis

In Computational Methods in Organometallic Catalysis: From Elementary Reactions to Mechanisms, distinguished chemist and author Yu Lan delivers a synthesis of the use of calculation methods and experimental techniques to improve the efficiency of reaction and yield of product and to uncover the factors that control the selectivity of product. Providing not only a theoretical overview of organometallic catalysis, the book also describes computational studies for the mechanism of transition-metal-assisted reactions.

You'll learn about Ni-, Pd-, Pt-, Co-, Rh-, Ir-, Fe-, Ru-, Mn-, Cu-, Ag-, and Au- catalysis. You'll also discover many of the experimental and theoretical advances in organometallic catalysis reported in the recent literature. The book summarizes and generalizes the advances made in the mechanistic study of organometallic catalysis.

Readers will also benefit from the inclusion of:

• A thorough introduction to computational organometallic chemistry, including a brief history of the discipline and the use of computational tools to study the mechanism of organometallic chemistry
• An exploration of computational methods in organometallic chemistry, including density functional theory methods and basis sets and their application in mechanism studies
• A practical discussion of elementary reactions in organometallic chemistry, including coordination and dissociation, oxidative addition, reductive elimination, insertion, elimination, transmetallation, and metathesis
• A concise treatment of the theoretical study of transition-metal catalysis.

Perfect for organic, catalytic, complex, and structural chemists, Computational Methods in Organometallic Catalysis will also earn a place in the libraries of theoretical chemists seeking a one-stop organometallic catalysis resource with a focus on the mechanism of transition-metal-assisted reactions.

Dr. Yu Lan, Distinguished Professor of Henan Province, is a part of the faculty of Zhengzhou University, China, and a 2016 recipient of the Chinese Chemical Society Award for Outstanding Yong Chemist. His current research focus is on theoretical study of the mechanism and selectivity for transition-metal catalysis.

Discover recent advances in the mechanistic study of organometallic catalysis

In Computational Methods in Organometallic Catalysis: From Elementary Reactions to Mechanisms, distinguished chemist and author Yu Lan delivers a synthesis of the use of calculation methods and experimental techniques to improve the efficiency of reaction and yield of product and to uncover the factors that control the selectivity of product. Providing not only a theoretical overview of organometallic catalysis, the book also describes computational studies for the mechanism of transition-metal-assisted reactions.

You'll learn about Ni-, Pd-, Pt-, Co-, Rh-, Ir-, Fe-, Ru-, Mn-, Cu-, Ag-, and Au- catalysis. You'll also discover many of the experimental and theoretical advances in organometallic catalysis reported in the recent literature. The book summarizes and generalizes the advances made in the mechanistic study of organometallic catalysis.

Readers will also benefit from the inclusion of:

• A thorough introduction to computational organometallic chemistry, including a brief history of the discipline and the use of computational tools to study the mechanism of organometallic chemistry
• An exploration of computational methods in organometallic chemistry, including density functional theory methods and basis sets and their application in mechanism studies
• A practical discussion of elementary reactions in organometallic chemistry, including coordination and dissociation, oxidative addition, reductive elimination, insertion, elimination, transmetallation, and metathesis
• A concise treatment of the theoretical study of transition-metal catalysis.

Perfect for organic, catalytic, complex, and structural chemists, Computational Methods in Organometallic Catalysis will also earn a place in the libraries of theoretical chemists seeking a one-stop organometallic catalysis resource with a focus on the mechanism of transition-metal-assisted reactions.

Foreword xv

Preface xvii

Part I Theoretical View of Organometallic Catalysis 1

1 Introduction of Computational Organometallic Chemistry 3

1.1 Overview of Organometallic Chemistry 3

1.1.1 General View of Organometallic Chemistry 3

1.1.2 A Brief History of Organometallic Chemistry 6

1.2 Using Computational Tool to Study the Organometallic ChemistryMechanism 8

1.2.1 Mechanism of Transition Metal Catalysis 8

1.2.2 Mechanistic Study of Transition Metal Catalysis by Theoretical Methods 10

References 13

2 Computational Methods in Organometallic Chemistry 19

2.1 Introduction of Computational Methods 19

2.1.1 The History of Quantum Chemistry Computational Methods 19

2.1.2 Post-HF Methods 21

2.2 Density Functional Theory (DFT) Methods 23

2.2.1 Overview of Density Functional Theory Methods 23

2.2.2 Jacob's Ladder of Density Functionals 25

2.2.3 The Second Rung in Jacob's Ladder of Density Functionals 25

2.2.4 The Third Rung in Jacob's Ladder of Density Functionals 26

2.2.5 The Fourth Rung in Jacob's Ladder of Density Functionals 26

2.2.6 The Fifth Rung in Jacob's Ladder of Density Functionals 26

2.2.7 Correction of Dispersion Interaction in Organic Systems 27

2.3 Basis Set and Its Application in Mechanism Studies 29

2.3.1 General View of Basis Set 29

2.3.2 Pople's Basis Sets 30

2.3.3 Polarization Functions 31

2.3.4 Diffuse Functions 31

2.3.5 Correlation-Consistent Basis Sets 31

2.3.6 Pseudo Potential Basis Sets 32

2.4 Solvent Effect 33

2.5 How to Choose a Method in Computational Organometallic Chemistry 34

2.5.1 Why DFT Method Is Chosen 34

2.5.2 How to Choose a Density Functional 34

2.5.3 How to Choose a Basis Set 36

2.6 Revealing a Mechanism for An Organometallic Reaction by Theoretical Calculations 37

2.7 Overview of Popular Computational Programs 37

2.8 The Limitation of Current Computational Methods 40

2.8.1 The Accuracy of DFT Methods 40

2.8.2 Exact Solvation Effect 41

2.8.3 Evaluation of Entropy Effect 41

2.8.4 The Computation of Excited State and High Spin State 41

2.8.5 Speculation on the Reaction Mechanism 41

References 42

3 Elementary Reactions in Organometallic Chemistry 51

3.1 General View of Elementary Reactions in Organometallic Chemistry 51

3.2 Coordination and Dissociation 52

3.2.1 Coordination Bond and Coordination 52

3.2.2 Dissociation 55

3.2.3 Ligand Exchange 57

3.3 Oxidative Addition 59

3.3.1 Concerted Oxidative Addition 60

3.3.2 Substitution-type Oxidative Addition 62

3.3.3 Radical-type Addition 67

3.3.4 Oxidative Cyclization 68

3.4 Reductive Elimination 70

3.4.1 Concerted Reductive Elimination 71

3.4.2 Substitution-type Reductive Elimination 73

3.4.3 Radical-Substitution-type Reductive Elimination 74

3.4.4 Bimetallic Reductive Elimination 75

3.4.5 Eliminative Reduction 78

3.5 Insertion 78

3.5.1 1,2-Insertion 79

3.5.2 1,1-Insertion 80

3.5.3 Conjugative Insertion 83

3.5.4 Outer-Sphere Insertion 84

3.6 Elimination 86

3.6.1 -Elimination 86

3.6.2 -Elimi…