Front Cover

Advances in Organometallic Chemistry

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Contents

Contributors

Chapter One: Palladium-Mediated Organofluorine Chemistry

1. Introduction

2. CC Coupling Reactions of Fluorinated Reagents

2.1. Overview of catalytic CC coupling reactions of fluorinated derivatives

2.1.1. CC coupling of fluorinated alkyl derivatives

2.1.1.1. Radical reactions

2.1.1.2. Perfluoroalkyl groups in the Stille reaction

2.1.1.3. Introduction of fluorinated groups using the Negishi reaction

2.1.1.4. Introduction of fluorinated groups using the Suzuki reaction

2.1.1.5. Use of fluoroalkyl silanes as fluoroalkylating reagents

2.1.1.6. Other fluoroalkylating reagents: Fluoroalkyl copper

2.1.1.7. Allylic alkylation reactions

2.1.1.8. Catalysis through palladium mediated CH activation

2.1.1.9. Perfluoroalkylation of unsaturated molecules

2.1.2. CC coupling of fluorinated aryl derivatives

2.1.2.1. Heck reactions

2.1.2.2. Suzuki-Miyaura reactions

2.1.2.3. Stille reactions

2.1.2.4. Sonogashira reactions

2.1.3. CC coupling of fluorinated arenes

2.1.4. CC coupling of fluorinated alkenyls

2.2. The PdRF bond

2.2.1. PdAlkylF bonds

2.2.2. PdArF bonds

2.3. Elementary steps in organofluorine CC coupling palladium-catalyzed processes

2.3.1. Oxidative addition and related processes

2.3.1.1. Oxidative addition to Pd(0) compounds

2.3.1.2. Oxidation of Pd(II) compounds leading to organofluorine Pd(IV) derivatives

2.3.2. Transmetalation

2.3.2.1. The transmetalation step in the Stille reaction

2.3.2.2. Transmetalation equilibria between organogold and organopalladium complexes

2.3.2.3. The transmetalation step in the Negishi reaction

2.3.3. Reductive elimination

2.3.3.1. Reductive elimination from Pd(II) complexes

2.3.3.2. Reductive elimination from Pd(IV) complexes

2.3.4. 2,1-Insertion

2.3.5. 1,1-Insertion (migratory insertion)

3. CF Activation and Fluorination

3.1. Overview of catalytic CC and CX coupling reactions where a CF bond is cleaved

3.1.1. CC coupling reactions of fluorinated aryls

3.1.2. CC Coupling reactions of fluorinated alkenes

3.1.3. Allylic substitutions of a fluorine atom

3.1.4. Hydrodefluorination reactions

3.2. Overview of catalytic CF forming reactions

3.2.1. Pd-catalyzed fluorination with electrophilic fluorine sources

3.2.2. Pd-catalyzed fluorination with nucleophilic fluorine sources

3.3. The PdF bond

3.4. Oxidative addition of RF

3.5. β-F and α-F elimination

3.6. Other activation routes for CF cleavage

3.7. Reductive elimination of RF

4. Conclusion

Acknowledgment

References

Chapter Two: Normal and Abnormal N-Heterocyclic Carbene Ligands: Similarities and Differences of Mesoionic C-Donor Complexes

1. Introduction and General Considerations

2. Ligand Nomenclature: Abnormal or Mesoionic Carbene Complexes?

3. Electronic Considerations

4. Reactivity of Complexes with Sterically Comparable Ligands

4.1. Imidazolylidene complexes

4.1.1. Structure and electronics of normal versus abnormal mesoionic imidazolylidene complexes

4.1.2. Comparative evaluation of imidazolylidene complexes in hydrogenation catalysis and related transformations

4.1.3. Comparative evaluation of imidazolylidene complexes in cross-coupling catalysis

4.2. N,X-Heterocyclic carbene complexes

4.3. Triazolylidene complexes

4.4. Pyridylidene complexes

4.4.1. Monodentate pyridylidene complexes

4.4.2. Polydentate pyridylidene complexes

4.4.3. Catalytic applications of pyridylidene complexes

5. Conclusions and Outlook

Acknowledgments

References

Chapter Three: Synthesis and Applications in Catalysis of Metal Complexes with Chelating Phosphinosulfonate Ligands

1. Introduction

2. Synthetic Routes to Achiral and Racemic Phosphine Sulfonic Acid Prochelates

2.1. Preparation of phosphinoalkylsulfonates

2.2. Preparation of symmetrical phosphinoarylsulfonic acids

2.3. Preparation of racemic P-stereogenic phosphinoarylsulfonic acids

2.4. Preparation of miscellaneous sulfonate prochelates

2.4.1. Polysulfonated o-phosphinoarylsulfonates

2.4.2. Phosphinoarylsulfonates

2.4.3. Racemic ferrocenylphosphinosulfonate

2.4.4. Diazaphospholidinobenzenesulfonates

2.4.5. Imidazolium sulfonate zwitterions

3. Preparation of Scalemic Sulfonate Prochelates

3.1. Phosphinoferrocenesulfonates

3.2. P-chiral phosphinobenzenesulfonates

3.3. Enantiopure phosphinoethanesulfonates

3.4. Atropoisomeric phosphinobenzenesulfonates

3.5. Enantiopure imidazoliniumbenzenesulfonates

4. Applications of Sulfonate Prochelates in Coordination Chemistry

4.1. Transition metal complexes bearing phosphinosulfonate ligand

4.1.1. Palladium complexes

4.1.1.1. Neutral [(PO)2Pd] complexes

4.1.1.2. Anionic [Pd(PO)R]- complexes

4.1.1.3. Neutral allylic [Pd(PO)] complexes

4.1.1.4. Formation of palladium(alkyl)(PO) complexes

4.1.2. Nickel complexes

4.1.3. Platinum complexes

4.1.4. Rhodium and iridium complexes

4.1.5. Ruthenium complexes

4.2. Transition metal complexes bearing NHC-sulfonate ligand

5. Applications in Molecular Catalysis

5.1. Ruthenium-catalyzed activation of allylic alcohols

5.2. Hydrogenation/hydrogen (auto)transfers

5.2.1. Iridium-catalyzed hydrogenation of alkenes

5.2.2. Ruthenium-catalyzed hydrogenation of ketones

5.2.3. C(3)-alkylation of saturated amines through hydrogen autotransfer

5.3. Rhodium-catalyzed hydroformylation

5.4. Copper-catalyzed conjugate addition

5.5. Copper-catalyzed asymmetric allylic alkylation

5.6. Miscellaneous reactions catalyzed by phoshinesulfonate metal complexes

6. Application of Metal-Phosphinosulfonate Chelate Complexes in Polymerization

6.1. Oligo- and polymerization of ethylene

6.2. Copolymerization of ethylene with polar monomers

6.3. Copolymerization of ethylene with carbon monoxide

6.4. Copolymerization of polar monomers with carbon monoxide

7. Recent Contributions

8. Conclusions and Outlook

Acknowledgments

References

Chapter Four: The Mannich Route to Amino-Functionalized [3]Ferrocenophanes

1. Introduction

2. Prolog: Synthesis of Ansa-Zirconocenes by the Mannich Reaction

3. [3]Ferrocenophane Synthesis by the Mannich Route

4. [3]Ferrocenophane Derived N/P and P/P Chelate Ligands

5. [3]Ferrocenophanes in Bio-Organometallic Chemistry

6. Frustrated Lewis Pair Chemistry at the [3]Ferrocenophane Framework

7. Some Conclusions

Acknowledgments

References

Chapter Five: Organometallic Intermediates of Gold Catalysis

1. Introduction

2. Organogold Intermediates

2.1. π-Complexes

2.1.1. Alkene gold complexes

2.1.2. Arene gold complexes

2.1.3. Allene gold complexes

2.1.4. Alkyne gold complexes

2.2. Vinylic organogold complexes

2.3. Alkylgold complexes

2.4. Gold hydrides

2.5. Gem-diaurated complexes and gold acetylides

2.6. Gold carbenoids

2.7. Gold(III) intermediates

3. Conclusions

References

Index