Understanding organometallic reaction mechanisms and catalysis : computational and experimental tools /: computational and experimental tools. (2015)

• Record Type: Book
• Further Information: Note: Edited by Valentine P. Ananikov ; contributors, Vincenzo Barone [and twenty-seven others].
• Editors: Ananikov, Valentine P
• Other Names: Barone, Vincenzo 1964- contributor.
• Contents: 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 Spectros
• Publisher Details: Weinheim, Germany : Wiley-VCH
• Publication Date: 2015
• Copyright Date: 2015
• Extent: 1 online resource (402 pages), illustrations (some color)
• Subjects: 661.34; Ammonia; Catalysis; TECHNOLOGY & ENGINEERING -- Chemical & Biochemical; Ammonia; Catalysis; Electronic books
• Languages: English
• ISBNs: 9783527678211; 3527678212; 9783527678242; 3527678247; 3527335625; 9783527335626; 3527678220; 9783527678228; 3527678239; 9783527678235; 9781322095066
• Related ISBNs: 132209506X; 9783527335626; 9783527678228; 9783527678235; 9783527678211
• Notes: Note: Includes bibliographical references at the end of each chapters and index.; Note: Online resource; title from PDF title page (ebrary, viewed September 10, 2014).
• Access Rights: Legal Deposit; Only available on premises controlled by the deposit library and to one user at any one time; The Legal Deposit Libraries (Non-Print Works) Regulations (UK).
• Access Usage: Restricted: Printing from this resource is governed by The Legal Deposit Libraries (Non-Print Works) Regulations (UK) and UK copyright law currently in force.