Ligand Design in Metal Chemistry: Reactivity and Catalysis

The design of ancillary ligands used to modify the structural and reactivity properties of metal complexes has evolved into a rapidly expanding sub–discipline in inorganic and organometallic chemistry. Ancillary ligand design has figured directly in the discovery of new bonding motifs and stoichiometric reactivity, as well as in the development of new catalytic protocols that have had widespread positive impact on chemical synthesis on benchtop and industrial scales. Ligand Design in Metal Chemistry presents a collection of cutting–edge contributions from leaders in the field of ligand design, encompassing a broad spectrum of ancillary ligand classes and reactivity applications. Topics covered include: Key concepts in ligand design Redox non–innocent ligands Ligands for selective alkene metathesis Ligands in cross–coupling Ligand design in polymerization Ligand design in modern lanthanide chemistry Cooperative metal–ligand reactivity P,N Ligands for enantioselective hydrogenation Spiro–cyclic ligands in asymmetric catalysis This book will be a valuable reference for academic researchers and industry practitioners working in the field of ligand design, as well as those who work in the many areas in which the impact of ancillary ligand design has proven significant, for example synthetic organic chemistry, catalysis, medicinal chemistry,  polymer science and materials chemistry. INDICE: List of Contributors xii .Foreword by Stephen L. Buchwald xiv .Foreword by David Milstein xvi .Preface xvii .1 Key Concepts in Ligand Design: An Introduction 1Rylan J. Lundgren and Mark Stradiotto .1.1 Introduction 1 .1.2 Covalent bond classification and elementary bonding concepts 2 .1.3 Reactive versus ancillary ligands 4 .1.4 Strong – and weak –field ligands 4 .1.5 Trans effect 6 .1.6 Tolman electronic parameter 6 .1.7 Pearson acid base concept 8 .1.8 Multidenticity, ligand bite angle, and hemilability 8 .1.9 Quantifying ligand steric properties 10 .1.10 Cooperative and redox non –innocent ligands 12 .1.11 Conclusion 12 .References 13 .2 Catalyst Structure and Cis Trans Selectivity in Ruthenium –based Olefin Metathesis 15Brendan L. Quigley and Robert H. Grubbs .2.1 Introduction 15 .2.2 Metathesis reactions and mechanism 17 .2.3 Catalyst structure and E/Z selectivity 24 .2.4 Z –selective Ru –based metathesis catalysts 33 .2.5 Cyclometallated Z –selective metathesis catalysts 36 .2.6 Conclusions and future outlook 42 .References 43 .3 Ligands for Iridium –catalyzed Asymmetric Hydrogenation of Challenging Substrates 46Marc –André Müller and Andreas Pfaltz .3.1 Asymmetric hydrogenation 46 .3.2 Iridium catalysts based on heterobidentate ligands 49 .3.3 Mechanistic studies and derivation of a model for the enantioselective step 57 .3.4 Conclusion 63 .References 64 .4 Spiro Ligands for Asymmetric Catalysis 66Shou –Fei Zhu and Qi –Lin Zhou .4.1 Development of chiral spiro ligands 66 .4.2 Asymmetric hydrogenation 73 .4.3 Carbon carbon bond –forming reactions 85 .4.4 Carbon heteroatom bond –forming reactions 91 .4.5 Conclusion 98 .References 98 .5 Application of Sterically Demanding Phosphine Ligands in Palladium –Catalyzed Cross –Coupling leading to C(sp2) E Bond Formation (E = NH2 , OH, and F) 104Mark Stradiotto and Rylan J. Lundgren .5.1 Introduction 104 .5.2 Palladium –catalyzed selective monoarylation of ammonia 108 .5.3 Palladium –catalyzed selective hydroxylation of (hetero)aryl halides 117 .5.4 Palladium –catalyzed nucleophilic fluorination of (hetero)aryl (pseudo)halides 123 .5.5 Conclusions and outlook 129 .Acknowledgments 130 .References 131 .6 Pd –N –Heterocyclic Carbene Complexes in Cross –Coupling Applications 134Jennifer Lyn Farmer, Matthew Pompeo, and Michael G. Organ .6.1 Introduction 134 .6.2 N –heterocyclic carbenes as ligands for catalysis 135 .6.3 The relationship between N –heterocyclic carbene structure and reactivity 136 .6.4 Cross –coupling reactions leading to C C bonds that proceed through transmetalation 140 .6.5 Kumada Tamao Corriu 141 .6.6 Suzuki Miyaura 148 .6.7 Negishi coupling 163 .6.8 Conclusion 170 .References 171 .7 Redox Non –innocent Ligands: Reactivity and Catalysis 176Bas de Bruin, Pauline Gualco, and Nanda D. Paul .7.1 Introduction 176 .7.2 Strategy I. Redox non –innocent ligands used to modify the Lewis acid base properties of the metal 179 .7.3 Strategy II. Redox non –innocent ligands as electron reservoirs 181 .7.4 Strategy III. Cooperative ligand –centered reactivity based on redox active ligands 192 .7.5 Strategy IV. Cooperative substrate –centered radical –type reactivity based on redox non –innocent substrates 195 .7.6 Conclusion 200 .References 201 .8 Ligands for Iron –based Homogeneous Catalysts for the Asymmetric Hydrogenation of Ketones and Imines 205Demyan E. Prokopchuk, Samantha A. M. Smith, and Robert H. Morris .8.1 Introduction: from ligands for ruthenium to ligands for iron 205 .8.2 First generation iron catalysts with symmetrical [6.5.6– –P –N –N –P ligands 216 .8.3 Second generation iron catalysts with symmetrical [5.5.5– –P –N –N –P ligands 220 .8.4 Third generation iron catalysts with unsymmetrical [5.5.5– –P –NH –N –P ligands 227 .8.5 Conclusions 231 .Acknowledgments 232 .References 232 .9 Ambiphilic Ligands: Unusual Coordination and Reactivity Arising from Lewis Acid Moieties 237Ghenwa Bouhadir and Didier Bourissou .9.1 Introduction 237 .9.2 Design and structure of ambiphilic ligands 238 .9.3 Coordination of ambiphilic ligands 242 .9.4 Reactivity of metallic complexes deriving from ambiphilic ligands 251 .9.5 Conclusions and outlook 264 .References 266 .10 Ligand Design in Enantioselective Ring –opening Polymerization of Lactide 270Kimberly M. Osten, Dinesh C. Aluthge, and Parisa Mehrkhodavandi .10.1 Introduction 270 .10.2 Indium and zinc complexes bearing chiral diaminophenolate ligands 292 .10.3 Dinuclear indium complexes bearing chiral salen –type ligands 297 .10.4 Conclusions and future directions 301 .References 302 .11 Modern Applications of Trispyrazolylborate Ligands in Coinage Metal Catalysis 308Ana Caballero, M. Mar Díaz –Requejo, Manuel R. Fructos, Juan Urbano, and Pedro J. Pérez .11.1 Introduction 308 .11.2 Trispyrazolylborate ligands: main features 310 .11.3 Catalytic systems based on Tpx ML complexes (M=Cu, Ag) 311 .11.4 Conclusions 326 .Acknowledgments 326 .References 327 .12 Ligand Design in Modern Lanthanide Chemistry 330David P. Mills and Stephen T. Liddle .12.1 Introduction and scope of the review 330 .12.2 C –donor ligands 333 .12.3 N –donor ligands 344 .12.4 P –donor ligands 349 .12.5 Multiple bonds 350 .12.6 Conclusions 356 .Notes 357 .References 357 .13 Tight Bite Angle N,O –Chelates. Amidates, Ureates and Beyond 364Scott A. Ryken, Philippa R. Payne, and Laurel L. Schafer .13.1 Introduction 364 .13.2 Applications in reactivity and catalysis 377 .13.3 Conclusions 400 .References 401 .Index 406

• ISBN: 978-1-118-83983-6
• Editorial: Wiley–Blackwell
• Encuadernacion: Cartoné
• Páginas: 448
• Fecha Publicación: 14/10/2016
• Nº Volúmenes: 1
• Idioma: Inglés