Pincer and Pincer-Type Complexes (eBook)

Kálmán J. Szabó is professor at the Department of Organic Chemistry at the Arrhenius Laboratory, Stockholm University, Sweden, since 2003. He obtained his PhD at Lund University, Sweden, with Prof. Salo Gronowitz in 1993, and did his postdoctoral research with Prof. Dieter Cremer at University of Gothenburg, Sweden. Szabó's research interest involves theoretical and experimental aspects of organic synthesis, organometallic chemistry and homogenous catalysis. He has developed synthetically useful catalytic transformations, including asymmetric catalysis, based on Pd, Ir, Cu and Ti complexes with a particular attention to C-C, C-B and C-Sn formation reactions. Currently his research interest focuses on C-H functionalization processes and catalytic organofluoride chemistry. He is the author of more than 100 publications and several book chapters. Ola F. Wendt is professor of Inorganic Chemistry since 2010 and Head of the Centre for Analysis and Synthesis at Lund University, Sweden. He received his PhD with Prof. Lars Ivar Elding at und University in 1997 and then moved to Caltech in Pasadena (USA) to do postdoctoral work with Prof. John Bercaw for two years. His major research interests revolve around organotransition metal chemistry, homogeneous catalysis and mechanistic studies. He has developed numerous pincer based complexes with palladium, platinum and iridium, and has studied their applications and mechanisms in cross-coupling reactions and small molecule activation. Since 2010 he is an elected fellow of the Royal Physiographic Society in Lund. He is the author of more than 70 publications and review articles.

Preface

CATALYSIS BY PINCER COMPLEXES: SYNTHESIS OF ESTERS, AMIDES, AND PEPTIDES
Introduction and Background
Bond Activatio by Metal-Ligand Cooperation
Synthesis of Esters
Synthesis of Amides
Synthesis of Peptides from Beta-Amino Alcohols
Concluding Remarks

THE ROLE OF REDOX PROCESSES IN REACTIONS CATALYZED BY NICKEL AND PALLADIUM COMPLEXES WITH ANIONIC PINCER LIGANDS
Introduction
Pincer Complexes of Ni, Pd, and Pt in Oxidation States Different from II
Catalytic Reactions Involving Redox Processes in the Pincer-Metal Framework
Concluding Remarks

APPENDED FUNCTIONALITY IN PINCER LIGANDS
Introduction
Appended Functionality Coplanar with the Pincer Chelate
Appended Functionality Not Coplanar to the Pincer Chelate
Future Outlook and Summary

C-C, C-O, AND C-B BOND FORMATION BY PINCER COMPLEXES INCLUDING ASYMMETRIC CATALYSIS
Introduction - Pros and Cons of Using Pincer Complexes in Catalysis
Reaction of Imines and Isocyanoacetates
C-H Functionalization of Organonitriles
Reactions Involving Hypervalent Iodines
Summary and Outlook

NICKEL-CATALYZED CROSS-COUPLING REACTIONS
Introduction
Carbon-Carbon Bond-Forming Reactions
Carbon-Heteroatom Bond-Forming Reactions
Summary and Outlook

PSiP TRANSITION-METAL PINCER COMPLEXES: SYNTHESIS, BOND ACTIVATION, AND CATALYSIS
Introduction
PSiP Ligand Syntheses
Group 8 Metal PSiP Chemistry
Group 9 Metal PSiP Chemistry
Group 10 Metal PSiP Chemistry
Group 11 Metal PSiP Chemistry
Alternative Silyl Pincers
Summary

ELECTRONIC STRUCTURES OF REDUCED MANGANESE, IRON, AND COBALT COMPLEXES BEARING REDOX-ACTIVE BIS(IMINO)PYRIDINE PINCER LIGANDS
Introduction
Reduced Manganese, Iron, and Cobalt Complexes with Redox-Active Bis(imino)pyridines
Conclusions and Outlook

PINCER COMPLEXES WITH SATURATED FRAMEWORKS: SYNTHESIS AND APPLICATIONS
Introduction
Synthesis of the Ligands
Synthesis and Coordination Behavior of Carbometallated PC(sp3)P Complexes
Reactivity and Catalytic Applications of PC(sp3) Complexes

HEAVIER GROUP 14 ELEMENTS-BASED PINCER COMPLEXES IN CATALYTIC SYNTHETIC TRANSFORMATIONS OF UNSATURATED HYDROCARBONS
Introduction
Synthesis of Palladium Complexes Bearing PXP-Pincer Ligands (X=Si, Ge, Sn)
Hydrocarboxylation
Reductive Aldol Type Reaction
Dehydrogenative Borylation
Synthesis and Reaction of n2-(Si-H)Pd(0) Complex as an Equivalent to PSiP-Palladium Hydride Complexes
Conclusions

EXPERIMENTAL AND THEORETICAL ASPECTS OF PALLADIUM PINCER-CATALYZED C-C CROSS-COUPLING REACTIONS
C-C Cross-Coupling Reactions - An Indispensable Tool for the Synthesis of Complex Organic Molecules
Palladium Pincer Complexes as C-C Cross-Coupling Catalysts
The Role of Palladium Pincer Complexes in Heck Reactions
Computational Investigations on the Thermal Feasibility of PdII/PdIV Cycles of Palladium Pincer-Catalyzed Heck Reactions
Theoretical Investigations on a Pincer-Catalyzed Negishi Cross-Coupling Reaction
Concluding Remarks

REACTIONS OF SQUARE-PLANAR d8 PINCER COMPLEXES WITH OXYGEN AN HYDROGEN
Introduction
Insertion of Molecular Oxygen into Late-Transition Metal Hydride Bonds
Hydrogenolysis of Late-Transition Metal Hydroxide and Alkoxide Complexes
Summary

Index