Chapter
Chapter 2 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-Innocent Ligand
2.1.1 Electronic Structure of Free Carbenes
2.1.2 Electronic Structure of Metallocarbenes
2.2 Theoretical Models and Methods
2.3 Design of Catalyst with Non-redox-Active Metal and Non-Innocent Ligand
2.3.1 The Proposed Catalyst: a Coordinatively Saturated Ca(II) Complex
2.3.2 Potential Energy Surface of the [(PDI)Ca(THF)3] Catalyzed C-H Bond Alkylation of MeCH2Ph by Unsubstituted N2CH2 Diazocarbene
2.3.3 [(PDI)Ca(THF)3]-Catalyzed C-H Bond Alkylation of MeCH2Ph by Donor-Donor (D/D) Diazocarbene N2CPh2
2.4 Conclusions and Perspectives
Chapter 3 Using Metal Vinylidene Complexes to Probe the Partnership Between Theory and Experiment
3.1.1 The Partnership between Theory and Experiment
3.1.2 Transition-Metal-Stabilized Vinylidenes
3.2 Project Planning in Organometallic Chemistry
3.2.1 Experimental Methodologies
3.2.2 Computational Methodologies
3.3.1 Mechanism of Rhodium-Mediated Alkyne to Vinylidene Transformation
3.3.2 Using Ligand Assistance to Form Ruthenium-Vinylidene Complexes
3.3.3 Vinylidenes in Gold Catalysis
3.3.4 Metal Effects on the Alkyne/Vinylidene Tautomer Preference
3.4 The Benefits of Synergy and Partnerships
Chapter 4 Ligand, Additive, and Solvent Effects in Palladium Catalysis - Mechanistic Studies En Route to Catalyst Design
4.2 The Effect of Solvent in Palladium-Catalyzed Cross Coupling and on the Nature of the Catalytically Active Species
4.3 Common Additives in Palladium-Catalyzed Cross-Coupling Reactions - Effect on (Pre)catalyst and Active Catalytic Species
4.4 Pd(I) Dimer: Only Precatalyst or Also Catalyst?
4.5 Investigation of Key Catalytic Intermediates in High-Oxidation-State Palladium Chemistry
Chapter 5 Computational Studies on Sigmatropic Rearrangements via π-Activation by Palladium and Gold Catalysts
5.1.1 Sigmatropic Rearrangements
5.1.2 Metal-Catalyzed Sigmatropic Rearrangements
5.2 Palladium as a Catalyst
5.2.1 Palladium Alkene Activation
5.2.1.1 [3,3]-Sigmatropic Rearrangements
5.2.1.2 [2,3]-Sigmatropic Rearrangements
5.2.2 Palladium Alkyne Activation
5.3.1 Gold Alkene Activation
5.3.1.1 [3,3]-Sigmatropic Rearrangements
5.3.2 Gold Alkyne Activation
5.3.2.1 [3,3]-Sigmatropic Rearrangements
Chapter 6 Theoretical Insights into Transition Metal-Catalyzed Reactions of Carbon Dioxide
6.3 Hydrogenation of CO2 with H2
6.4 Coupling Reactions of CO2 and Epoxides
6.5 Reduction of CO2 with Organoborons
6.6 Carboxylation of Olefins with CO2
6.7 Hydrocarboxylation of Olefins with CO2 and H2
Chapter 7 Catalytically Enhanced NMR of Heterogeneously Catalyzed Hydrogenations
7.2 Parahydrogen and PHIP Basics
7.3 PHIP as a Mechanistic Tool in Homogeneous Catalysis
7.3.1 PHIP-Enhanced NMR of Reaction Products
7.3.2 PHIP Studies of Reaction Intermediates
7.3.3 Activation of H2 and Structure and Dynamics of Metal Dihydride Complexes
7.4 PHIP-Enhanced NMR and Heterogeneous Catalysis
7.4.1 PHIP with Immobilized Metal Complexes
7.4.2 PHIP with Supported Metal Catalysts
7.4.3 Model Calculations Related to Underlying Chemistry in PHIP
7.5 Summary and Conclusions
Chapter 8 Combined Use of Both Experimental and Theoretical Methods in the Exploration of Reaction Mechanisms in Catalysis by Transition Metals
8.1.1 Hammett Methodology
8.1.2 Kinetic Isotope Effects
8.1.3 Competition Experiments
8.2 Recent DFT Developments of Relevance to Transition Metal Catalysis
8.2.1 Computational Efficiency
8.2.4 Effective Core Potentials
8.2.5 Connecting Theory with Experiment
8.3.1 Rhodium-Catalyzed Decarbonylation of Aldehydes
8.3.2 Iridium-Catalyzed Alkylation of Alcohols with Amines
8.3.3 Palladium-Catalyzed Allylic C-H Alkylation
8.3.4 Ruthenium-Catalyzed Amidation of Alcohols
Chapter 9 Is There Something New Under the Sun? Myths and Facts in the Analysis of Catalytic Cycles
9.1.2 A Brief History of Catalysis
9.2 Kinetics Based on Rate Constants or Energies
9.2.2 TOF Calculation of Any Cycle
9.2.3 TOF in the E-Representation
9.3 Application: Cross-Coupling with a Bidentate Pd Complex
9.4 A Century of Sabatier's Genius Idea
9.5 Theory and Practice of Catalysis, Including Concentration Effects
9.5.1 Application: Negishi Cross-Coupling with a Ni Complex
9.5.2 Can a Reaction Be Catalyzed in Both Directions?
9.6.1 Finding the RDStates
9.6.2 Finding the Irreversible Steps
9.7.1 The Last Myth: Defining the TOF
9.7.2 Final Words about the E-Representation
Chapter 10 Computational Tools for Structure, Spectroscopy and Thermochemistry
10.2.1 Potential Energy Surface: Molecular Structure, Transition States, and Reaction Paths
10.2.2 DFT and Hybrid Approaches for Organometallic Systems
10.2.3 Description of Environment
10.3 Spectroscopic Techniques
10.3.1 Rotational Spectroscopy
10.3.1.1 Identification of Conformers/Tautomers
10.3.1.2 Accurate Equilibrium Structures
10.3.2 Vibrational Spectroscopy
10.3.2.2 Infrared and Raman Intensities
10.3.2.3 Effective Treatment of Fermi Resonances
10.3.2.5 Approximate Methods: Hybrid Force Fields
10.3.2.6 Approximate Methods: Reduced Dimensionality VPT2
10.3.3 Electronic Spectroscopy
10.3.3.1 General Framework for Time-Independent and Time-Dependent Computations of Vibronic Spectra
10.3.3.2 Approximate Description of Excited State PES
10.4 Applications and Case Studies
10.4.1 Thermodynamics and Vibrational Spectroscopy Beyond Harmonic Approximation: Glycine and Its Metal Complexes
10.4.1.1 Accurate Results for Isolated Glycine from Hybrid CC/DFT Computations
10.4.1.2 Glycine Adsorbed on the (100) Silicon Surface
10.4.1.3 Glycine-Metal Binding
10.4.2 Optical Properties of Organometallic Systems
10.4.2.1 Metal Complexation effects on the Structure and UV-Vis Spectra of Alizarin
10.4.2.2 Luminescent Organometallic Complexes of Technological Interest
10.4.3 Interplay of Different Effects: The Case of Chlorophyll-a
10.5 Conclusions and Future Developments
Chapter 11 Computational Modeling of Graphene Systems Containing Transition Metal Atoms and Clusters
11.2 Quantum Chemical Modeling and Benchmarking
11.2.1 Electron Correlation Methods
11.2.1.1 Truncated Coupled Cluster Methods
11.2.1.2 Truncated Quadratic Configuration Interaction Methods
11.2.1.3 Methods of Møller-Plesset Perturbation Theory
11.2.2 Dispersion-Accounting DFT Methods
11.2.2.1 Empirically Corrected DFT Methods
11.2.2.2 Density Functionals with Nonlocal Correlation Term
11.2.3 Database and Benchmarking Considerations
11.2.3.1 S22, S66, and Related Databases
11.2.3.2 Databases of Relatively Large Intermolecular Systems
11.2.3.3 DFT Methods Benchmarking against Systems with Transition Metal Species
11.2.4 Outlook on Database and Benchmarking
11.3 Representative Studies of Graphene Systems with Transition Metals
11.3.2 Pristine Graphene as a Substrate for Transition Metal Particles
11.3.2.1 Transition Metal Adatoms on Pristine Graphene
11.3.2.2 Metal Clusters or Nanoparticles on Pristine Graphene
11.3.3 Defective or Doped Graphene as a Support for Transition Metal Particles
11.3.3.1 Transition Metal Adatoms on Doped or Defective Graphene
11.3.3.2 Transition Metal Clusters on Doped or Defective Graphene
11.3.4 Studies of Complex Graphene Systems with Transition Metals
11.3.5 Modeling Chemical Transformations in Graphene/Transition Metal Systems
Understanding Organometallic Reaction Mechanisms and Catalysis
：Computational and Experimental Tools
Disclaimer: Any content in publications that violate the sovereignty, the constitution or regulations of the PRC is not accepted or approved by CNPIEC.
