This book presents recent advances in dinuclear complexes in which the metal-metal cooperative effect operates for obtaining substrate activation and high performance catalysts. Catalysis continues to be a fast expanding area to design efficient tools in synthesis and in industrial chemistry. It allows performing syntheses with short reaction times, atom economy, reduced consumption of energy and loss of reagents, and low level of wastes. Dinuclear complexes are known to be more efficient than the mononuclear analogues for the reaction rates and the selectivities. This book analyses the latest research, focusing on the key concepts, in building and using these dinuclear complexes. The book is aimed at researchers, graduate students and chemists at all levels in academia and industry.
Author(s): Philippe Kalck
Series: Topics in Organometallic Chemistry, 70
Publisher: Springer
Year: 2023
Language: English
Pages: 240
City: Cham
Preface
References
Contents
Dinuclear Reactivity of One Metal Exalted by the Second One
1 Introduction
2 Mechanisms in Which Only One Metal Center Undergoes Oxidative Addition Reaction
2.1 Two Electrons Oxidative Addition on One Metal Center
2.1.1 Direct 2 Electrons Oxidative Addition on M´
2.1.2 Oxidative Addition on One Metal Center Followed by Migration to the Second Metal Center
2.1.3 Sequential Double Oxidative Addition
2.2 Preliminary Coordination of a Part of the Substrate onto the Other Metal Center
3 Migratory Insertion on a Single Metal Center
3.1 Bimetallic Alkene Polymerization
3.1.1 Ti-Ti complexes
3.1.2 Zr-Zr Complexes
3.1.3 Ti-Cr Complexes
3.1.4 Ni-Ni Complexes
3.1.5 Ni-Zn Complexes
3.2 Alkyne Activation
3.3 Metathesis Using Ru-Ru Complexes
4 Reductive Elimination
4.1 Pd-Pd-Catalyzed Functionalization of C-H Reductive Elimination
4.1.1 Pd(III)-Pd(III) Intermediates
4.1.2 Pd(II)-Pd(II) Precursors (C-H Activation and Migratory Insertion)
5 Miscellaneous Reactions
5.1 Michael Reactions (Chiral Nucleophilic Attack)
5.2 Nucleophilic Attack on Alkynes
5.3 Ni2 and Hydrosilylation (Double Oxidative Addition)
5.4 Ni2 and Azobenzenes from Aryl Azides
5.5 Ru2 in the Kharasch Reaction (1 Electron Oxidative Addition)
5.6 Au2 in Ring Closure Reactions
5.7 Pd-Ru in Hydrodefluorination
5.8 Ir2 NHC Complexes in Reductions with MeOH
5.9 Bichromophoric Ru-Pd and Ir-Pd Catalysts
5.10 Heterogeneous Systems
6 Conclusions
References
Chemical Transformations in Heterobimetallic Complexes Facilitated by the Second Coordination Sphere
1 Introduction
2 Stoichiometric Bond Activation Mediated by the Second Coordination Sphere
3 Catalysis Mediated by the Second Coordination Sphere
3.1 Switchable Systems
3.1.1 Redox-Switchable Systems
3.1.2 Cation-Responsive Systems
4 Conclusions
References
Role of a Redox-Active Ligand Close to a Dinuclear Activating Framework
1 Introduction
2 Hydrogenases-Bio-Inspired Dinuclear Complexes Featuring a Redox Ligand
2.1 Complexes with a Non-Metal Based Redox Ligand
2.1.1 Introduction of a Redox Ligand Through Monodentate Coordination
2.1.2 Introduction of a Redox Ligand via Chelating Coordination
2.1.3 Redox Bridging Ligands
2.2 Complexes with a Metal-Based Redox Ligand
3 Illustrations of Various Bimetallic Complexes with a Redox Ligand for Molecular Activation
4 Conclusions
References
Dinuclear Reactivity Between the Two Metal Centers
1 Introduction
2 Mechanisms in Which Each Metal Center Is Involved in a 1e-1e Reaction
2.1 Absence of Bridging Ligands
2.2 Bimetallic Complexes with Redox Innocent Bridging Ligands
2.3 Redox Active Bridging Ligands
3 Mechanisms in Which Only One Metal Center Is Involved in a 1e Reaction
4 Conclusions
References
Magnetism in Binuclear Compounds: Theoretical Insights
1 Introduction
2 Model Hamiltonians and Their Extraction from Theoretical Calculations
2.1 Why Model Hamiltonians Are Mandatory for the Description of Magnetic Systems?
2.2 Theoretical Tools for the Extraction of Model Interactions
2.2.1 Theoretical Calculations
2.2.2 The Effective Hamiltonian Theory
3 Mononuclear Compounds
4 Binuclear Compounds
4.1 Giant-Spin Approximation and Its Generalization to a Block-Spin Approach
4.2 The Multispin Approximation
4.2.1 Isotropic Exchange
4.2.2 Anisotropic Exchange Interactions
5 Concluding Remarks
References
