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ÊéÃû Atomically-Precise Methods for Synthesis of Solid Catalysts ×÷Õß Sophie Hermans, Thierry Visart de Bocarme Ò³Êý 316 ³ö°æÉç RSC Print ISBN: 978-1-84973-829-3 PDF eISBN: 978-1-78262-843-9 DOI:10.1039/9781782628439 Ŀ¼Contents Chapter 1 Synthesis of Well-defined Solid Catalysts by Surface Organometallic Chemistry 1 1.1 Introduction 1 1.2 Grafting Sites of the Support 3 1.3 Formation of Grafted Organometallic Complexes by Reaction with One Hydroxyl Group 6 1.3.1 Reaction of Metal Alkyl Complexes 6 1.3.2 Reactivity of Metal Alkylidenes or Alkylidynes 8 1.4 Further Reactions of Surface Species Formed by Reaction of an Organometallic Compound with One Hydroxyl Group 10 1.4.1 Further Reactions with Hydroxyl Groups 10 1.4.2 a-H, b-H and g-H Abstraction 11 1.4.3 Reaction with Hydrogen 12 1.4.4 Reaction with Other Molecules 14 1.5 Formation of Cationic Complexes on the Surface 15 1.6 Applications in Catalysis 17 1.6.1 Hydrogenolysis of Alkanes 17 1.6.2 Alkane Metathesis 18 1.6.3 Ethylene to Propene by Tungsten Hydride 18 1.6.4 Olefin Metathesis 19 1.6.5 Trimerization of Ethylene 19 1.6.6 Epoxidation and Deperoxidation Reactions 20 1.7 Activation of Ammonia and Nitrogen 21 1.8 Conclusion 22 References 22 1.2.3 NHC Ligands 10 1.2.4 Nitrogen Ligands 13 1.2.5 Palladacyclic Complexes 15 1.3 Cross-Coupling in Aqueous Media Using Hydrophobic Ligands 17 1.3.1 Surfactant-Free Reactions 17 1.3.2 Surfactant-Promoted Reactions 20 1.3.2.1 Cationic Surfactants 21 1.3.2.2 Anionic Surfactants 22 1.3.2.3 Nonionic Surfactants 22 1.4 Heterogeneous Catalysts in Aqueous Media 25 1.4.1 Supported Palladium¨CLigand Complexes 25 1.4.1.1 Polymer-Supported Palladium Complexes 25 1.4.1.2 Palladium Complexes Supported on Inorganic Materials 27 1.4.2 Nanoparticle-Catalyzed Coupling 29 1.4.2.1 Unsupported Palladium Nanoparticle Catalysts 29 1.4.2.2 Polymer-Supported Nanoparticles 30 1.4.2.3 Inorganic-Supported Nanoparticle Catalysts 33 1.5 Special Reaction Conditions 35 1.5.1 Microwave Heating 35 1.5.2 Ultrasound 36 1.5.3 Thermomorphic Reaction Control 36 VI Contents Chapter 2 Zeolite-supported Molecular Metal Complex Catalysts 27 Isao Ogino 2.1 Introduction 27 2.2 Synthesis 29 2.2.1 Synthesis by an Ion-exchange Method 29 2.2.2 Synthesis by a Chemical Vapor Deposition Method 30 2.2.3 Synthesis by the Surface Organometallic Chemistry Approach 31 2.3 Characterization Techniques 31 2.4 Guide for the Synthesis and Characterization of Supported Molecular Metal Complexes with a High Degree of Structural Uniformity 33 2.4.1 Types of Zeolite for Support Materials 33 2.4.2 Precursor Metal Complexes 38 2.4.3 Spectroscopic Characterization Techniques to Examine Structural Uniformity 41 2.5 Molecular Chemistry of Zeolite-supported Metal Complex Catalysts 41 2.5.1 Reactivity of Supported Metal Complexes 41 2.5.2 Catalytic Cycle 46 2.6 Conclusions and Future Directions 48 References 50 Chapter 3 Bimetallic Supported Catalysts from Single-source Precursors 55 Sophie Hermans 3.1 Introduction 55 3.2 Heteronuclear Species as Heterometallic Catalysts Precursors 57 3.2.1 Complexes with Heterometallic M¨CM0 Metal¨CMetal Bond 57 3.2.2 Ions Pairs 58 3.2.3 Heterometallic Complexes with Bridging Ligands 59 3.2.4 Other Bimetallic Combinations 61 3.2.5 Mixed-metal Precursors of Bulk Phases 61 3.3 Clusters as Precursors 64 3.3.1 Definition 64 3.3.2 Synthesis 65 viii Contents Downloaded on 14/11/2014 02:06:16. Published on 19 November 2014 on http://pubs.rsc.org | doi:10.1039/9781782628439-FP007 View Online |
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