Polar Organometallic Reagents - Synthesis, Structure, Properties and Applications

Outlines recent advances in the field of polar organometallic chemistry, particularly in the context of the emergent areas of synergic and cooperative species.
 
Polar Organometallic Reagents provides a critical overview of developments in the field of modern polar organometallic chemistry. With a particular focus on the emergent area of synergic heterometallic reagents, this timely volume describes our attempts to understand recently developed polar organometallics and their application in a range of new directions. Contributions from leading researchers present new synthetic work and discuss recent advances in characterization techniques, synthetic applications, and mechanistic understanding of heterometallic complexes.
 
In-depth chapters provide detailed information on fundamental, structural, and theoretical aspects of polar organometallic chemistry while articulating the need and rationale for the advent of new reagents. Topics include alkali and alkaline earth organometallics, synergy and cooperativity, cationic p-block clusters and other developments in main group catalysis, synthetic trends in alkenyl copper, ate complex and borylmetal chemistry, non-traditional reaction environments, and trends in developing greener processes. Designed to keep readers updated with the latest progress in the field, this much-needed book:
* Includes an introductory chapter outlining the development of synergic bases and the logic behind their creation
* Highlights the role of solid-state structural work in elucidating the bonding and reactivity displayed by modern polar organometallics
* Examines the use of calculations in catalyst design and plotting more sustainable reaction pathways
* Discusses modern trends in solution techniques that have achieved new insights into the structures of active species
* Presents striking advances in the ease of handling of polar organometallics and the emergence of main group catalysis
* Polar Organometallic Reagents is essential reading for researchers in chemical disciplines including synthetic inorganic and coordination chemistry, main group chemistry, organometallic chemistry, organic synthesis and catalysis.

List of contents

Preface xi
 
List of Contributors xv
 
Acknowledgements xvii
 
1 The Road to Aromatic Functionalization by Mixed-metal Ate Chemistry 1
 
Masanori Shigeno, Andrew J. Peel, Andrew E. H. Wheatley, and Yoshinori Kondo
 
1.1 Introduction 1
 
1.2 Deprotonation of Aromatics 2
 
1.2.1 Monometallic Bases 2
 
1.2.2 Bimetallic Bases 7
 
1.2.2.1 Group 1/1 Reagents 7
 
1.2.2.2 Group 1/2 Reagents 11
 
1.3 Aromatic Ate Complex Chemistry: Metal/Halogen Exchange 13
 
1.3.1 Introduction 13
 
1.3.2 Zincates 13
 
1.3.3 Cuprates 17
 
1.3.4 Solid-phase Synthesis 24
 
1.4 Deprotonation Using Ate Complexes 25
 
1.4.1 Introduction 25
 
1.4.2 Zincates 26
 
1.4.3 Cadmates 29
 
1.4.4 Aluminates 30
 
1.4.5 Cuprates 32
 
1.4.6 Argentates 39
 
1.5 Concluding Remarks 41
 
References 42
 
2 Structural Evidence for Synergistic Bimetallic Main Group Bases 49
 
Robert E. Mulvey and Stuart D. Robertson
 
2.1 General Introduction 49
 
2.2 Homometallic Bases 51
 
2.2.1 Carbanionic Lithium Reagents 51
 
2.2.2 Heavier Carbanionic Alkali Metal Reagents 56
 
2.2.3 Alkali Metal Amides 58
 
2.3 Heterometallic Bases 60
 
2.3.1 Heteroalkali Metal Bases 60
 
2.3.2 Alkali Metal Magnesiate Chemistry 64
 
2.3.3 Early Signs of Synergistic Behaviour in Zincate Chemistry 64
 
2.3.4 Lithium TMP-Zincate Chemistry 66
 
2.3.5 Sodium TMP-Zincate Chemistry 73
 
2.3.6 Lithium Chloride (Turbo Charged) TMP-Zinc Chemistry 78
 
2.3.7 Indirect TMP Zincation 79
 
2.3.8 Alkali Metal Group 13 Ates 80
 
2.3.9 Bimetallic Complexes Without an Alkali Metal Component 85
 
2.4 Outlook 91
 
References 91
 
3 Turbo Charging Group 2 Reagents for Metathesis, Metalation, and Catalysis 97
 
Michael S. Hill, Anne-Frédérique Pécharman, and Andrew S. S. Wilson
 
3.1 Introduction and Historical Context: Monometallic s-block Reagents and Their Utility 97
 
3.2 Heterobimetallic Reagents for Selective Metalation 100
 
3.2.1 Ate Complexes and Superbases 100
 
3.2.2 Lithium, Sodium, Potassium Magnesiates, MMgX3 101
 
3.2.3 Salt Effects and Magnesiate Formation 107
 
3.2.3.1 'Turbo-Grignards' for Selective Metalation 108
 
3.2.3.2 Turbo-Hauser Bases 112
 
3.2.4 Ate Complexes of the Heavier Alkaline Earth Elements Ca, Sr, and Ba 114
 
3.2.4.1 Alkyl Calciate, Strontiate, and Bariate Derivatives, MM'R3 (M = Li, Na, K; M' = Ca, Sr, Ba; R = alkyl) 115
 
3.2.4.2 Alkoxo and Aryloxo Calciate, Strontiate, and Bariate Derivatives, MM' (OR/Ar)3 (M = Li, Na, K; M' = Ca, Sr, Ba) 115
 
3.2.4.3 Amido Calciate, Strontiate, and Bariate Derivatives, MM'(OR/Ar)3 (M = Li, Na, K; M' = Ca, Sr, Ba) 116
 
3.3 Homogeneous Catalysis by s-block Reagents 117
 
3.4 Outlook: Turbo Charging the Turbo Reagents and Prospects for Catalysis 120
 
References 121
 
4 Mechanisms in Heterobimetallic Reactivity: Experimental and Computational Insights for Catalyst Design in Small Molecule Activation and Polymer Synthesis 133
 
Frances N. Singer and Antoine Buchard
 
4.1 Introduction and Scope of the Chapter 133
 
4.2 Small Molecule Activation and Catalysis 135
 
4.2.1 Hydrogen Activation 135
 
4.2.2 Dinitrogen Activation 147
 
4.2.3 CO2 Activation 150
 
4.3 Polymerization Catalysis 152
 
4.3.1 Olefin polymerization 152
 
4.3.1.1 Metallocene-based Heterobimetallic Catalysts 154
 
4.3.1.2 Constrained G

About the author

Andrew Wheatley, Professor of Materials Chemistry, Yusuf Hamied Department of Chemistry, University of Cambridge, UK. His research is focused on understanding the structure, synthesis and reactivity of mixed-metal organometallics, catalysts and composite materials. Masanobu Uchiyama, Professor, Graduate School of Pharmaceutical Sciences, The University of Tokyo, Japan, and Professor, Research Initiative for Supra-Materials (RISM) at Shinshu University, Japan (Cross Appointment). His research interests include development of innovative synthetic processes, new materials, and new functions based on integration of theoretical calculations and elements chemistry.

Summary

Outlines recent advances in the field of polar organometallic chemistry, particularly in the context of the emergent areas of synergic and cooperative species.

Polar Organometallic Reagents provides a critical overview of developments in the field of modern polar organometallic chemistry. With a particular focus on the emergent area of synergic heterometallic reagents, this timely volume describes our attempts to understand recently developed polar organometallics and their application in a range of new directions. Contributions from leading researchers present new synthetic work and discuss recent advances in characterization techniques, synthetic applications, and mechanistic understanding of heterometallic complexes.

In-depth chapters provide detailed information on fundamental, structural, and theoretical aspects of polar organometallic chemistry while articulating the need and rationale for the advent of new reagents. Topics include alkali and alkaline earth organometallics, synergy and cooperativity, cationic p-block clusters and other developments in main group catalysis, synthetic trends in alkenyl copper, ate complex and borylmetal chemistry, non-traditional reaction environments, and trends in developing greener processes. Designed to keep readers updated with the latest progress in the field, this much-needed book:
* Includes an introductory chapter outlining the development of synergic bases and the logic behind their creation
* Highlights the role of solid-state structural work in elucidating the bonding and reactivity displayed by modern polar organometallics
* Examines the use of calculations in catalyst design and plotting more sustainable reaction pathways
* Discusses modern trends in solution techniques that have achieved new insights into the structures of active species
* Presents striking advances in the ease of handling of polar organometallics and the emergence of main group catalysis
* Polar Organometallic Reagents is essential reading for researchers in chemical disciplines including synthetic inorganic and coordination chemistry, main group chemistry, organometallic chemistry, organic synthesis and catalysis.

Product details

• Authors: Masanobu Uchiyama, Masanobu (The University of Tokyo Uchiyama, a Wheatley, Andrew Wheatley, Andrew E. H. Wheatley, Andrew E. H. (University of Cambridge Wheatley, Andrew E. H. Uchiyama Wheatley, Andrew Uchiyama Wheatley, Andrew Williard Wheatley
• Assisted by: Andrew E H Wheatley (Editor), Uchiyama (Editor), Uchiyama (Editor), Masanobu Uchiyama (Editor), Andre Wheatley (Editor), Andrew Wheatley (Editor), Andrew E. H. Wheatley (Editor), Wheatley Andrew E. H. (Editor), Paul Williard (Editor)
• Publisher: Wiley, John and Sons Ltd
• Languages: English
• Product format: Hardback
• Released: 30.06.2021
• EAN: 9781119448822
• ISBN: 978-1-119-44882-2
• No. of pages: 416
• Subjects: Natural sciences, medicine, IT, technology > Chemistry > Organic chemistry; Chemie, Spektroskopie, ORGANOMETALLIC CHEMISTRY, Katalyse, chemistry, Catalysis, spectroscopy, Metallorganische Verbindungen, Organometallchemie