Understanding Organometallic Reaction Mechanisms and Catalysis

Preface

MECHANISMS OF METAL-MEDIATED C-N COUPLING PROCESSES: A SYNERGEISTIC RELATIONSHIP BETWEEN GAS-PHASE EXPERIMENTS AND COMPUTATIONAL CHEMISTRY
Introduction
From Metal-Carbon to Carbon-Nitrogen Bonds
From Metal-Nitrogen to Carbon-Nitrogen Bonds
Conclusion and Perspectives

FUNDAMENTAL ASPECTS OF THE METAL-CATALYZED C-H BOND FUNCTIONALIZATION BY DIAZOCARBENES: GUIDING PRINCIPLES FOR DESIGN OF CATALYST WITH NON-REDOX-ACTIVE METAL (SUCH AS CA) AND NON-INNOVENT LIGAND
Introduction
Theoretical Models and Methods
Design of Catalyst with Non-Redox-Active Metal and Non-Innocent Ligand
Conclusions and Perspectives

USING METAL VINYLIDENE COMPLEXES TO PROBE THE PARTNERSHIP BETWEEN THEORY AND EXPERIMENT
Introduction
Procect Planning in Organometallic Chemistry
Case Studies
The Benefits of Synergy and Partnerships

LIGAND, ADDITIVE, AND SOLVENT EFFECTS IN PALLADIUM CATALYSIS - MECHANISTIC STUDIES EN ROUTE TO CATALYST DESIGN
Introduction
The Effect of Solvent in Palladium-Catalyzed Cross Coupling and on the Nature of the Catalytically Active Species
Common Additives in Palladium-Catalyzed Cross-Coupling Reactions - Effect on (Pre)catalyst and Active Catalytic Species
Pd(I) Dimer: Only Precatalyst or Also Catalyst?
Investigation of Key Catalytic Intermediates in High-Oxidation-State Palladium Chemistry
Concluding Remarks

COMPUTATIONAL STUDIES ON SIGMATROPIC REARRANGEMENTS VIA PI-ACTIVATION BY PALLADIUM AND GOLD CATALYSTS
Introduction
Palladium as a Catalyst
Gold as a Catalyst
Concluding Remarks

THEORETICAL INSIGHTS INTO TRANSITION METAL-CATALYZED REACTIONS OF CARBON DIOXIDE
Introduction
Theoretical Methods
Hydrogenation of CO2 with H2
Coupling Reactions of CO2 and Epoxides
Reduction of CO2 with Organoborons
Carboxylation of Olefins with CO2
Summary

CATALYTICALLY ENHANCED NMR OF HETEROGENEOUSLY CATALYZED HYDROGENATIONS
Introduction
Parahydrogen and PHIP Basics
PHIP as a Mechanistic Tool in Homogeneous Catalysis
PHIP-Enhanced NMR of Reaction Products
PHIP-Enhanced NMR and Heterogeneous Catalysis
Summary and Conclusions

COMBINED USE OF BOTH EXPERIMENTAL AND THEORETICAL METHODS IN THE EXPLORATION OF REACTION MECHANISMS IN CATALYSIS BY TRANSITION METALS
Introduction
Recent DFT Developments of Relevance to Transition Metal Catalysis
Case Studies
Conclusions

IS THERE SOMETHING NEW UNDER THE SUN? MYTHS AND FACTS IN THE ANALYSIS OF CATALYTIC CYCLES
Introduction
Kinetics Based on Rate Constants or Energies
Application: Cross-Coupling with a Bidentate Pd Complex
A Century of Sabatier's Genius Idea
Theory and Practice of Catalysis, Including Concentration Effects
RDStep, RDStates
Conclusion

COMPUTATIONAL TOOLS FOR STRUCTURE, SPECTROSCOPY AND THERMOCHEMISTRY
Introduction
Basic Concepts
Spectroscopic Techniques
Applications and Case Studies
Conclusions and Future Developments

COMPUTATIONAL MODELING OF GRAPHENE SYSTEMS CONTAINING TRANSITION METAL ATOMS AND CLUSTERS
Introduction
Quantum Chemical Modeling and Benchmarking
Representative Studies of Graphene Systems with Transition Metals
Conclusions

Index