Understanding Organometallic Reaction Mechanisms and Catalysis Computational and Experimental Tools

List of Contributors XI

Preface XV

1 Mechanisms of Metal-Mediated C–N 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 Carbon–Nitrogen Bonds 2

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

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

1.2.3 C–N 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 C–H 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 C–H Bond Alkylation of MeCH2Ph by Unsubstituted N2CH2 Diazocarbene 27

2.3.3 [(PDI)Ca(THF)3]-Catalyzed C–H Bond Alkylation of MeCH2Ph by Donor–Donor (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 Ruthenium–Vinylidene 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 Dioxide 121
Ting Fan and Zhenyang Lin

6.1 Introduction 121

6.2 Theoretical Methods 122

6.3 Hydrogenation of CO2 with H2 122

6.4 Coupling Reactions of CO2 and Epoxides 127

6.5 Reduction of CO2 with Organoborons 131

6.6 Carboxylation of Olefins with CO2 134

6.7 Hydrocarboxylation of Olefins with CO2 and H2 134

6.8 Summary 137

Acknowledgment 139

References 139

7 Catalytically Enhanced NMR of Heterogeneously Catalyzed Hydrogenations 145
Vladimir V. Zhivonitko, Kirill V. Kovtunov, Ivan V. Skovpin, Danila A. Barskiy, Oleg G. Salnikov, and Igor V. Koptyug

7.1 Introduction 145

7.2 Parahydrogen and PHIP Basics 146

7.3 PHIP as a Mechanistic Tool in Homogeneous Catalysis 149

7.3.1 PHIP-Enhanced NMR of Reaction Products 150

7.3.2 PHIP Studies of Reaction Intermediates 152

7.3.3 Activation of H2 and Structure and Dynamics of Metal Dihydride Complexes 153

7.4 PHIP-Enhanced NMR and Heterogeneous Catalysis 155

7.4.1 PHIP with Immobilized Metal Complexes 155

7.4.2 PHIP with Supported Metal Catalysts 164

7.4.3 Model Calculations Related to Underlying Chemistry in PHIP 173

7.5 Summary and Conclusions 180

Acknowledgments 180

References 181

8 Combined Use of Both Experimental and Theoretical Methods in the Exploration of Reaction Mechanisms in Catalysis by Transition Metals 187
Daniel Lupp, Niels Johan Christensen, and Peter Fristrup

8.1 Introduction 187

8.1.1 Hammett Methodology 187

8.1.2 Kinetic Isotope Effects 188

8.1.3 Competition Experiments 189

8.2 Recent DFT Developments of Relevance to Transition Metal Catalysis 190

8.2.1 Computational Efficiency 191

8.2.2 Dispersion Effects 193

8.2.3 Solvation 195

8.2.4 Effective Core Potentials 196

8.2.5 Connecting Theory with Experiment 197

8.3 Case Studies 197

8.3.1 Rhodium-Catalyzed Decarbonylation of Aldehydes 198

8.3.2 Iridium-Catalyzed Alkylation of Alcohols with Amines 203

8.3.3 Palladium-Catalyzed Allylic C–H Alkylation 205

8.3.4 Ruthenium-Catalyzed Amidation of Alcohols 209

8.4 Conclusions 213

Acknowledgments 214

References 214

9 Is There Something New Under the Sun? Myths and Facts in the Analysis of Catalytic Cycles 217
Sebastian Kozuch

9.1 Introduction 217

9.1.1 Prologue 217

9.1.2 A Brief History of Catalysis 217

9.2 Kinetics Based on Rate Constants or Energies 218

9.2.1 Kinetic Graphs 220

9.2.2 TOF Calculation of Any Cycle 222

9.2.3 TOF in the E-Representation 225

9.3 Application: Cross-Coupling with a Bidentate Pd Complex 227

9.4 A Century of Sabatier’s Genius Idea 230

9.5 Theory and Practice of Catalysis, Including Concentration Effects 232

9.5.1 Application: Negishi Cross-Coupling with a Ni Complex 233

9.5.2 Can a Reaction Be Catalyzed in Both Directions? 236

9.5.3 The Power Law 239

9.6 RDStep, RDStates 239

9.6.1 Finding the RDStates 242

9.6.2 Finding the Irreversible Steps 243

9.7 Conclusion 244

9.7.1 The Last Myth: Defining the TOF 244

9.7.2 FinalWords about the E-Representation 245

References 246

10 Computational Tools for Structure, Spectroscopy and Thermochemistry 249
Vincenzo Barone, Malgorzata Biczysko, and Ivan Carnimeo

10.1 Introduction 249

10.2 Basic Concepts 251

10.2.1 Potential Energy Surface: Molecular Structure, Transition States, and Reaction Paths 251

10.2.2 DFT and Hybrid Approaches for Organometallic Systems 254

10.2.3 Description of Environment 257

10.3 Spectroscopic Techniques 260

10.3.1 Rotational Spectroscopy 261

10.3.3 Electronic Spectroscopy 280

10.4 Applications and Case Studies 287

10.4.1 Thermodynamics and Vibrational Spectroscopy Beyond Harmonic Approximation: Glycine and Its Metal Complexes 287

10.4.2 Optical Properties of Organometallic Systems 297

10.4.3 Interplay of Different Effects: The Case of Chlorophyll-a 302

10.5 Conclusions and Future Developments 308

Acknowledgments 309

References 309

11 ComputationalModeling of Graphene Systems Containing Transition Metal Atoms and Clusters 321
Mikhail V. Polynski and Valentine P. Ananikov

11.1 Introduction 321

11.2 Quantum Chemical Modeling and Benchmarking 322

11.2.1 Electron Correlation Methods 322

11.2.2 Dispersion-Accounting DFT Methods 324

11.2.3 Database and Benchmarking Considerations 334

11.2.4 Outlook on Database and Benchmarking 340

11.3 Representative Studies of Graphene Systems with Transition Metals 341

11.3.1 Graphene Models 341

11.3.2 Pristine Graphene as a Substrate for Transition Metal Particles 342

11.3.3 Defective or Doped Graphene as a Support for Transition Metal Particles 347

11.3.4 Studies of Complex Graphene Systems with Transition Metals 352

11.3.5 Modeling Chemical Transformations in Graphene/Transition Metal Systems 355

11.4 Conclusions 362

Acknowledgments 363

List of Abbreviations 363

References 365

Index 375