Frustrated Lewis Pairs

Preface
Contents
1 Frustrated Lewis Pair Catalysis: An Introduction
1.1 Introduction
1.2 FLP Hydrogenations
1.2.1 The Beginning
1.2.2 Broadening the Substrate Scope
1.2.3 Functional-Group Tolerance
1.2.4 Catalyst Variation
1.2.5 Heterogeneous Hydrogenation Catalysis
1.2.6 Asymmetric Hydrogenation
1.3 Other Catalysis with FLPs
1.3.1 Hydrosilylation
1.3.2 Transfer Hydrogenation
1.3.3 Hydroboration
1.3.4 Amination
1.3.5 Hydroarylation
1.3.6 C–H Borylation
1.3.7 Polymerization
1.3.8 CO2 Reduction
1.3.9 C–F Derivatization
1.4 Future Directions
References
2 Frustrated Lewis Pair Catalyzed Asymmetric Reactions
2.1 Introduction
2.2 Asymmetric Hydrogenation
2.2.1 Asymmetric Hydrogenation of Imines and Related Substrates
2.2.2 Asymmetric Hydrogenations of N-Heterocyclic Compounds
2.2.3 Asymmetric Hydrogenations of Silyl Enol Ethers
2.2.4 Asymmetric Hydrogenations of Ketones and Enones
2.3 Asymmetric Hydrosilylation
2.4 Asymmetric Transfer Hydrogenation
2.5 Miscellaneous
2.6 Summary
References
3 FLP Reduction of Carbon Monoxide and Related Reactions
3.1 Introduction
3.2 Synergic FLP Binding to NO, CO, and Related Molecules
3.3 Metal-Free FLP Reduction and Coupling of Carbon Monoxide
3.4 Reaction of P/B/B FLPs with Carbon Monoxide: Formation of Macrocyclic Oligomers
3.5 Reaction of Carbon Monoxide at d0-Metallocene Cations
3.6 Conclusions
References
4 FLP-Mediated C–H-Activation
4.1 Introduction
4.2 C–H Functionalization by Transition Metal Complexes
4.3 FLP Transformations: A Kinetic Concept
4.4 Functionalization of C–H Bonds Through Electrophilic Activation
4.4.1 Electrophilic Borylation Starting from Haloboranes
4.4.2 Electrophilic Borylation Starting from Hydroboranes
4.4.3 Electrophilic Silylation
4.5 Concerted Activation by FLPs
4.5.1 Activation of Alkenes and Alkynes
4.5.2 Activation of Alkanes
4.6 Catalytic C–H Borylation by FLPs
4.6.1 C–H Activation of Arenes with Aminoborane FLPs
4.6.2 Towards Practical Metal-Free C–H Borylation Methodologies
4.7 Isodesmic Borylation: Auto-Assembled FLPs
4.8 Frustrated Lewis Radicals
4.9 Concluding Remarks
References
5 Mechanistic Insight into the Hydrogen Activation by Frustrated Lewis Pairs
5.1 Introduction
5.2 Types of FLPs
5.2.1 Boron and Aluminum as Lewis Acid Centers
5.2.2 Nitrogen, Phosphorus, and Oxygen as Lewis Base Centers
5.3 Mechanistic Studies Using DFT Calculations
5.3.1 LA–LB Complexation
5.3.2 Transition State and Reaction Kinetics
5.3.3 Engineering FLP Reactivity
5.3.4 Ethereal Solvents as Lewis Bases
5.3.5 The Role of Water Molecules
5.4 Mechanistic Studies Using AIMD Simulation
5.4.1 Transition State Characterization by Ab Initio Molecular Dynamics Simulations
5.4.2 AIMD Simulation of Solvated Ion-Pairs
5.4.3 Free Energy Landscape of the FLP Catalyzed H2 Activation
5.4.4 Participation of Multiple Solvent Molecules
5.5 Lewis-Pair-Functionalized Metal–Organic Frameworks (MOFs) and Their Applications
5.5.1 Computationally Proposed LP-Functionalized UiO-66 for CO2 Hydrogenation
5.5.2 AIMD Simulations on LP-Functionalized MOFs
5.6 Summary and Outlook
References
6 Lewis Acidic Boranes in Frustrated Lewis Pair Chemistry
6.1 Introduction
6.2 Synthetic Routes to Boranes
6.2.1 Homoleptic Halogenated Triaryl Boranes
6.2.2 Heteroleptic Halogenated Triaryl Boranes
6.3 Boranes with Reduced Lewis Acidity Compared with B(C6F5)3
6.4 Water-Tolerant Boranes
6.4.1 Modifying Reaction Conditions
6.4.2 Design of Novel Boranes
6.5 Chiral Boranes in FLP Catalysis
6.5.1 Synthesis
6.5.2 Salt Metathesis
6.5.3 Hydroboration
6.6 Summary
References
7 Heterogeneous Catalysis by Frustrated Lewis Pairs
7.1 Introduction
7.2 Semi-Immobilised Frustrated Lewis Pairs
7.2.1 Solid Lewis Base with a Soluble Lewis Acid
7.2.2 Solid Lewis Acid with a Soluble Lewis Base
7.3 Fully Immobilised FLPs
7.3.1 Solid-Supported Intramolecular FLPs
7.3.2 Solid Lewis Acid and Base
7.3.3 Metal-Organic Frameworks (MOFs)
7.3.4 Mesoporous Silica
7.3.5 Zeolites
7.3.6 Polyoxometalate Clusters
7.3.7 Surface (Interfacial) FLPs
7.4 Concluding Remarks
References
8 Lewis Acid−Base Pairs for Polymerization Catalysis: Recent Progress and Perspectives
8.1 Introduction
8.2 Lewis Pair Polymerization of Polar Vinyl Monomers
8.2.1 Petroleum-Based Polar Vinyl Monomers
8.2.2 Biomass-Derived Polar Vinyl Monomers
8.3 Lewis Pair-Mediated Ring-Opening (Co)Polymerization
8.4 Summary and Outlook
References
9 Frustrated Lewis Pairs Based on Transition Metals
9.1 Introduction
9.2 TMFLPs with One Transition Metal Center
9.2.1 Early and Mid-Transition Metals
9.2.2 Late Transition Metals
9.2.3 Rare-Earth elements
9.3 Frustrated Lewis Pairs and Related Systems based on Two Transition Metals
9.3.1 Transition Metal Only Frustrated Lewis Pairs (TMOFLPs)
9.3.2 Polarized heterobimetallic compounds
9.4 Conclusion
References
10 Radicals in Frustrated Lewis Pair Chemistry
10.1 Introduction
10.1.1 Radicals in FLP Chemistry
10.2 Reactions of FLP Systems with Radical Substrates
10.2.1 Nitrous Oxide (N2O)
10.2.2 Nitric Oxide (NO)
10.2.3 9,10-Phenanthrenequinone
10.3 Radical Generation Using a ‘Pseudo-FLP’
10.3.1 Reduction of ‘FLP’ Lewis Acids B(C6F5)3 and Al(C6F5)3
10.3.2 Pseudo-FLP Reactivity
10.4 Single-Electron Transfer Within Frustrated Lewis Pair Systems
10.4.1 SET to Generate Radical Ion Pairs
10.4.2 Photoinduced Versus Thermal Single-Electron Transfer
10.4.3 Applications in Synthesis
10.5 Concluding Remarks
References
11 Frustrated Lewis Pair Pedagogy: Expanding Core Undergraduate Curriculum and Reinforcing Fundamental Thermodynamic Concepts
11.1 Introduction
11.2 Methods
11.2.1 Participants
11.2.2 Structure of CHEM 151B
11.2.3 Incorporation of FLP Material
11.2.4 Assessments
11.2.5 Questionnaire
11.3 Results
11.3.1 Incorporation of FLP Material
11.3.2 Influence of FLP Coverage on Understanding Thermodynamics
11.4 Discussion
11.5 Conclusions
Appendix 1
References
Index