Understanding Organometallic Reaction Mechanisms and Catalysis Experimental and Computational Tools

Exploring and highlighting the new horizons in the studies of reaction mechanisms that open joint application of experimental studies and theoretical calculations is the goal of this book.

The latest insights and developments in the mechanistic studies of organometallic reactions and catalytic processes are presented and reviewed. The book adopts a unique approach, exemplifying how to use experiments, spectroscopy measurements, and computational methods to reveal reaction pathways and molecular structures of catalysts, rather than concentrating solely on one discipline. The result is a deeper understanding of the underlying reaction mechanism and correlation between molecular structure and reactivity. The contributions represent a wealth of first-hand information from renowned experts working in these disciplines, covering such topics as activation of small molecules, C-C and C-Heteroatom bonds formation, cross-coupling reactions, carbon dioxide converison, homogeneous and heterogeneous transition metal catalysis and metal-graphene systems. With the knowledge gained, the reader will be able to improve existing reaction protocols and rationally design more efficient catalysts or selective reactions.

An indispensable source of information for synthetic, analytical, and theoretical chemists in academia and industry.

Autorentext
Valentine Ananikov received his Ph.D. degree in 1999, Habilitation in 2003, and was appointed Professor and Laboratory Head of the ND Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences in 2005. In 2008 he was elected as a Member of Russian Academy of Sciences. In 2012 he became Professor of Chemistry, Department of Moscow State University. In 2013 he has received a Megagrant of Saint Petersburg State University and was appointed as Head of Laboratory of Cluster Catalysis.
Valentine Ananikov was a recipient of the Russian State Prize for Outstanding Achievements in Science and Technology in 2004, a Science Support Foundation award in 2005, a Russian Academy of Sciences Medal in 2000. He was named a Liebig Lecturer by German Chemical Society in 2010, and was awarded the Balandin Prize for outstanding achievements in the field of catalysis in 2010. His scientific interests are focused on development of new concepts in transition metal and nanoparticle catalysis, sustainable organic synthesis and new methodology for mechanistic studies of complex chemical transformations. His research has been supported by grants of Russian Science Foundation, Russian Foundation of Basic Research and Grants of President of Russia.
Valentine Ananikov is a member of the International Advisory Boards of Advanced Synthesis & Catalysis, Organometallics, Chemistry - An Asian Journal and OpenChemistry.

Inhalt

List of Contributors XI

Preface XV

1 Mechanisms of Metal-Mediated CN Coupling Processes: A Synergistic Relationship between Gas-Phase Experiments and Computational Chemistry 1
Robert Kretschmer, Maria Schlangen, and Helmut Schwarz

1.1 Introduction 1

1.2 From Metal-Carbon to CarbonNitrogen Bonds 2

1.2.1 Thermal Reactions of Metal Carbide and Metal Methylidene Complexes with Ammonia 2

1.2.2 How Metals Control the CN Bond-Making Step in the Coupling of CH4 and NH3 4

1.2.3 CN Coupling via SN2 Reactions: Neutral Metal Atoms as a Novel Leaving Group 6

1.3 From Metal-Nitrogen to Carbon-Nitrogen Bonds 8

1.3.1 High-Valent Iron Nitride and Iron Imide Complexes 8

1.3.2 Metal-Mediated Hydroamination of an Unactivated Olefin by [Ni(NH2)]+ 11

1.4 Conclusion and Perspectives 12

Acknowledgments 14

References 14

2 Fundamental Aspects of theMetal-Catalyzed CH Bond Functionalization by Diazocarbenes: Guiding Principles for Design of Catalyst with Non-redox-Active Metal (Such as Ca) and Non-Innocent Ligand 17
Adrian Varela-Alvarez and Djamaladdin G. Musaev

2.1 Introduction 17

2.1.1 Electronic Structure of Free Carbenes 20

2.1.2 Electronic Structure of Metallocarbenes 22

2.2 TheoreticalModels andMethods 25

2.3 Design of Catalyst with Non-redox-Active Metal and Non-Innocent Ligand 26

2.3.1 The Proposed Catalyst: a Coordinatively Saturated Ca(II) Complex 26

2.3.2 Potential Energy Surface of the [(PDI)Ca(THF)3] Catalyzed CH Bond Alkylation of MeCH2Ph by Unsubstituted N2CH2 Diazocarbene 27

2.3.3 [(PDI)Ca(THF)3]-Catalyzed CH Bond Alkylation of MeCH2Ph by DonorDonor (D/D) Diazocarbene N2CPh2 32

2.4 Conclusions and Perspectives 35

Acknowledgment 37

References 37

3 Using Metal Vinylidene Complexes to Probe the Partnership Between Theory and Experiment 41
John M. Slattery, Jason M. Lynam, and Natalie Fey

3.1 Introduction 41

3.1.1 The Partnership between Theory and Experiment 41

3.1.2 Transition-Metal-Stabilized Vinylidenes 42

3.2 Project Planning in Organometallic Chemistry 44

3.2.1 Experimental Methodologies 44

3.2.2 Computational Methodologies 46

3.3 Case Studies 49

3.3.1 Mechanism of Rhodium-Mediated Alkyne to Vinylidene Transformation 50

3.3.2 Using Ligand Assistance to Form RutheniumVinylidene Complexes 54

3.3.3 Vinylidenes in Gold Catalysis 58

3.3.4 Metal Effects on the Alkyne/Vinylidene Tautomer Preference 61

3.4 The Benefits of Synergy and Partnerships 63

References 64

4 Ligand, Additive, and Solvent Effects in Palladium Catalysis Mechanistic Studies En Route to Catalyst Design 69
Franziska Schoenebeck

4.1 Introduction 69

4.2 The Effect of Solvent in Palladium-Catalyzed Cross Coupling and on the Nature of the Catalytically Active Species 71

4.3 Common Additives in Palladium-Catalyzed Cross-Coupling Reactions Effect on (Pre)catalyst and Active Catalytic Species 75

4.4 Pd(I) Dimer: Only Precatalyst or Also Catalyst? 79

4.5 Investigation of Key Catalytic Intermediates in High-Oxidation-State Palladium Chemistry 81

4.6 Concluding Remarks 87

References 88

5 Computational Studies on Sigmatropic Rearrangements via Pi-Activation by Palladium and Gold Catalysts 93
Osvaldo Gutierrez and Marisa C. Kozlowski

5.1 Introduction 93

5.1.1 Sigmatropic Rearrangements 93

5.1.2 Metal-Catalyzed Sigmatropic Rearrangements 93

5.2 Palladium as a Catalyst 94

5.2.1 Palladium Alkene Activation 94

5.2.2 Palladium Alkyne Activation 103

5.3 Gold as a Catalyst 103

5.3.1 Gold Alkene Activation 103

5.3.2 Gold Alkyne Activation 108

5.4 Concluding Remarks 117

References 117 **6 Theoretical Insights into Transition Metal-Catalyzed Reactions of Carbon Dioxid...