Activating Unreactive Substrates: The Role of Secondary Interactions

The use of secondary interactions for the activation of non-reactive substrates constitutes a new and modern approach in catalysis. This first comprehensive treatment of this important research field covers the entire field and reveals the links between the various chemical disciplines. It thus adopts an interdisciplinary approach, making it of interest to the whole chemical community. A must for organic, inorganic, catalytic and complex chemists, as well as those working with/on organometallics.

Table of Contents:
Preface XIII List of Contributors XV 1 Chemistry of Metalated Container Molecules 1 Berthold Kersting 1.1 Introduction 1 1.2 Metalated Container Molecules: A Brief Overview 2 1.3 Metalated Container Molecules of Binucleating Supporting Ligands 2 1.3.1 Synthesis 3 1.3.2 Coordination Chemistry of Binucleating Supporting Ligands 4 1.3.3 Effects of N-alkylation on the Molecular and Electronic Structures of the Complexes 5 1.3.4 The Ligand Matrix as a Medium 6 1.3.5 Variation, Coordination Modes and Activation of Coligands 7 1.3.6 Reactivity of the Complexes 10 1.4 Conclusions 12 References 13 2 The Chemistry of Superbasic Guanidines 17 Jörg Sundermeyer, Volker Raab, Ekatarina Gaoutchenova, Udo Garrelts, Nuri Abacilar, and Klaus Harms 2.1 Properties of the Guanidine Functionality 17 2.2 Design of Superbasic Proton Sponges 18 2.3 Some Perspectives in Proton Sponge Chemistry 20 2.4 Multidentate Superbasic Guanidine Ligands as Receptors for Metal Cations 22 2.5 The Chemistry of Guanidine Copper Complexes 24 2.6 The Chemistry of Guanidine Zinc Complexes 31 2.7 Conclusions 35 References 35 3 Iron Complexes and Dioxygen Activation 39 Thomas Nebe, Jing-Yuan Xu, and Siegfried Schindler 3.1 Introduction 39 3.2 Dinuclear Iron Peroxo Complexes 40 3.3 Tripodal Tetradentate Ligands and Derivatives 42 3.3.1 Tmpa 42 3.3.2 Uns-penp 44 3.4 Mononuclear Iron Peroxo Complexes 46 3.5 Mononuclear Iron Oxo Species 48 3.6 Work in Progress 49 3.7 Conclusions 49 References 50 4 Tuning of Structures and Properties of Bispidine Complexes 53 Peter Comba and Marion Kerscher 4.1 Introduction 53 4.2 Jahn–Teller Isomerism with Copper(II) Bispidines 55 4.3 Stabilization of High-spin Ferryl Complexes 59 4.4 Jahn–Teller-distorted Cobalt(III) Complexes 61 4.5 Conclusions 62 References 63 5 Novel Phosphorus and Nitrogen Donor Ligands Bearing Secondary Functionalities for Applications in Homogeneous Catalysis 65 Anna-Katharina Pleier, Yu Sun, Anett Schubert, Dirk Zabel, Claudia May, Andreas Reis, Gotthelf Wolmershäuser, and Werner R. Thiel 5.1 Introduction 65 5.2 Phosphine Ligands 66 5.2.1 Cooperative Effects for Ligand Self-organization 66 5.2.2 Phosphines with Pyrazole and Pyrimidine Substituents 72 5.3 Nitrogen Donor Ligands Without Phosphorus Sites 77 5.4 Conclusion 85 References 85 6 Square-Pyramidal Coordinated Phosphine Iron Fragments: A Tale of the Unexpected 89 Andreas Grohmann and Stephan Kohl 6.1 Introduction 89 6.2 Polyphosphine Ligands with Three and Four Coordinating Arms 91 6.3 C–P Bond Activation and Agostic Interactions in Iron Complexes of Polypodal Phosphine Ligands 92 6.4 Mechanistic Considerations 99 6.5 Conclusion 100 References 101 7 Regioselective Catalytic Activity of Complexes with NH,NR-substituted Heterocyclic Carbene Ligands 103 Siegfried R. Waldvogel, Anke Spurg, and F. Ekkehardt Hahn 7.1 Introduction 103 7.2 Concept of Regioselective Substrate Activation 103 7.3 Synthesis of Complexes with NH,NR-stabilized NHC Ligands 106 7.4 Preparation of Substrates for Catalytic Experiments 115 7.5 Catalysis Experiments 116 7.6 Conclusions and Summary 119 References 120 8 Functionalized Cycloheptatrienyl-Cyclopentadienyl Sandwich Complexes as Building Blocks in Metallo-supramolecular Chemistry 123 Matthias Tamm 8.1 Introduction 123 8.2 Syntheses and Electronic Structures of Group 4 Cycloheptatrienyl-Cyclopentadienyl Sandwich Complexes 124 8.3 Syntheses and Reactivity of ansa-Cycloheptatrienyl-Cyclopentadienyl Complexes 130 8.4 Ring-opening Reactions of ansa-Cycloheptatrienyl-Cyclopentadienyl Complexes 135 8.5 Phosphine-functionalized Cycloheptatrienyl-Cyclopentadienyl Sandwich Complexes 140 References 143 9 Monosaccharide Ligands in Organotitanium and Organozirconium Chemistry 147 Peter Kitaev, Daniela Zeysing, and Jürgen Heck 9.1 Introduction 147 9.2 Synthesis of Organotitanium Carbohydrate Compounds 147 9.3 Organotitanium Carbohydrate Compounds for Use in Catalytic Reactions: Polymerization of Ethylene 152 9.4 Intramolecular Hydroamination of Aminoalkenes 153 9.5 Organozirconium Carbohydrate Compounds 155 9.6 Amine Exchange 156 9.7 Chiral Recognition 157 9.7.1 Diels–Alder Reaction 159 9.7.2 Nucleophilic Addition 159 9.8 Conclusions 162 References 163 10 Reactions of C–F Bonds with Titanocene and Zirconocene: From Secondary Interaction via Bond Cleavage to Catalysis 165 Uwe Rosenthal, Vladimir V. Burlakov, Perdita Arndt, Anke Spannenberg, Ulrike Jäger-Fiedler, Marcus Klahn, and Marko Hapke 10.1 Introduction and Background 165 10.2 Secondary Interactions with C–F Bonds 166 10.2.1 Reactions of Metallacyclopropenes with B(C6F5)3 166 10.2.2 Reactions of Five-membered Metallacycles with B(C6F5)3 170 10.3 Formation of M–F Bonds 171 10.3.1 Stoichiometric Cleavage of C–F Bonds 171 10.3.2 Stoichiometric Formation by M–C Bond Cleavage and Exchange Reactions 174 10.4 Stoichiometric Formation of Zr–H Bonds 174 10.4.1 From Zr–F/Al–H to Zr–H/Al–F Bonds 174 10.5 Catalytic Formation of Zr–H Bonds 175 10.5.1 From Zr–F using Al–H to Zr–H and Al–F Bonds 175 10.5.2 Catalytic Ethene Polymerization 176 10.5.3 Catalytic Hydrodefluorination of Activated C–F Bonds 178 10.5.4 Hydrodefluorination of Nonactivated C–F Bonds by Diisobutylaluminumhydride via the Aluminum Cation [iBu2Al]þ 178 10.6 Conclusion 179 References 180 11 Bisazines in the Coordination Sphere of Early Transition Metals 183 Ruediger Beckhaus 11.1 Introduction 183 11.2 Results and Discussion 185 11.2.1 Formation of Molecular Architectures 185 11.2.2 Molecular Architectures Accompanied by Radical-induced C–C Coupling Reactions 195 11.2.3 Molecular Architectures Based on C–C Coupling Reactions Initiated by C–H Bond Activation Reactions 199 11.3 Conclusions and Future Directions 203 References 204 12 Bifunctional Molecular Systems with Pendant Bis(pentafluorophenyl)boryl Groups: From Intramolecular CH-activation to Heterolytic Dihydrogen Splitting 209 Michael Hill, Christoph Herrmann, Patrick Spies, Gerald Kehr, Klaus Bergander, Roland Fröhlich, and Gerhard Erker 12.1 Introduction 209 12.2 Bifunctional Zirconium/Boron Systems 210 12.3 Bifunctional Group 9 Metal/Boron Systems 216 12.4 Bifunctional Phosphorus/Boron Systems 223 12.5 Conclusions 228 References 228 13 Ruthenium-containing Polyoxotungstates: Structure and Redox Activity 231 Ulrich Kortz 13.1 Introduction 231 13.2 The Organoruthenium(II)-containing 49-Tungsto-8-Phosphate [{K(H2O)}3{Ru(p cymene)(H2O)}4P8W49O186(H2O)2]27_ 232 13.3 The Mono-Ruthenium(III)-substituted Keggin-Type 11-Tungstosilicate [a-SiW11O39RuIII(H2O)]5– and its Dimerization 236 13.4 Conclusions 241 References 242 14 From NO to Peroxide Activation by Model Iron(III) Complexes 245 Alicja Franke, Natalya Hessenauer-Ilicheva, Joo-Eun Jee, and Rudi van Eldik 14.1 Introduction 245 14.2 NO Activation by Fe(III) Complexes 246 14.2.1 Fe(III)-Porphyrins 246 14.2.2 Cytochrome P450 and Model Complexes 254 14.3 Peroxide Activation by Fe(III) Complexes 260 14.3.1 Cytochrome P450 262 14.3.2 Fe(III) Porphyrins 263 14.3.3 Catalytic Oxidation Cycle 266 14.4 Conclusions 271 References 272 15 Synthetic Nitrogen Fixation with Molybdenum and Tungsten Phosphine Complexes: New Developments 273 Gerald Stephan and Felix Tuczek 15.1 Introduction 273 15.2 Mechanistic Investigation of the Chatt Cycle 276 15.2.1 Protonation of N2 276 15.2.2 N–N Cleavage 278 15.2.3 Reactivity of Nitrido and Imido Complexes 280 15.2.4 DFT Calculations of the Chatt Cycle 282 15.3 New Phosphine and Mixed P/N Ligands for Synthetic Nitrogen Fixation 285 15.3.1 Tetraphos Ligands 285 15.3.2 Pentaphosphine Complexes 287 15.3.3 Mixed P/N Ligands 291 15.4 Summary and Conclusions 294 References 294 16 Directed C–H Functionalizations 297 Carsten Bolm 16.1 Introduction 297 16.2 Results and Discussion 300 16.3 Conclusions 307 References 307 17 Development of Novel Ruthenium and Iron Catalysts for Epoxidation with Hydrogen Peroxide 313 Man Kin Tse, Bianca Bitterlich, and Matthias Beller 17.1 Introduction 313 17.2 Development of Epoxidation Catalysts Using H2O2 314 17.2.1 Ruthenium-catalyzed Epoxidation 315 17.2.2 Biomimetic Iron-catalyzed Epoxidation 318 References 332 18 Pentacoordinating Bis(oxazoline) Ligands with Secondary Binding Sites 339 Caroline A. Schall, Michael Seitz, Anja Kaiser, and Oliver Reiser References 348 19 Flavin Photocatalysts with Substrate Binding Sites 349 Harald Schmaderer, Jiri Svoboda, and Burkhard König 19.1 Introduction 349 19.2 Templated Flavin Photoreductions 351 19.3 Templated Flavin Photooxidations 353 19.4 Summary and Outlook 355 References 356 20 New Catalytic Cu-, Pd- and Stoichiometric Mg-, Zn-Mediated Bond Activations 359 Tobias Thaler, Hongjun Ren, Nina Gommermann, Giuliano C. Clososki, Christoph J. Rohbogner, Stefan H. Wunderlich, and Paul Knochel 20.1 Introduction 359 20.2 Catalytic Activation 360 20.2.1 C–H Bond Activation for the Preparation of Condensed Polycyclic Alkaloids 360 20.2.2 Activation of Terminal Alkynes in a One-pot Three-component Enantioselective Synthesis of Propargylamines 363 20.3 Stoichiometric Activation 366 20.3.1 The Halogen-Magnesium Exchange 366 20.3.2 Selective Deprotonation Reactions with Magnesium and Zinc Amides 368 20.4 Summary 375 References 375 21 From Cobalt(II)-activated Molecular Oxygen to Hydroxymethyl-substituted Tetrahydrofurans 379 Bárbara Menéndez Pérez, Dominik Schuch, and Jens Hartung 21.1 Introduction [1] 379 21.2 Thermochemical Considerations 381 21.3 Cobalt(II)-Diketonate Complexes 382 21.4 Reactivity 383 21.5 Stereoselectivity Survey 388 21.6 A Derivative of Magnosalicin 390 21.7 Expanding the Scope 391 21.8 Concluding Remarks 393 References 395 22 Regiodivergent Epoxide Opening 397 Andreas Gansäuer, Florian Keller, Chun-An Fan, and Peter Karbaum 22.1 Epoxide Opening via Nucleophilic Substitution: Limitations Arising from the SN2-mechanism 397 22.2 Regiodivergent Epoxide Opening (REO): Mechanistic Implications, Synthetic Potential, and Aspects of Catalyst Design 398 22.3 Reductive Epoxide Opening via Electron Transfer from Titanocene(III) Reagents 400 22.3.1 Mechanism of Reductive Epoxide Opening: Predetermined for REO! 401 22.4 Synthetic Realization of Titanocene-catalyzed REO 402 References and Notes 407 23 Supramolecular Containers: Host-guest Chemistry and Reactivity 411 Markus Albrecht 23.1 Introduction 411 23.2 M4L4Tetrahedra 412 23.2.1 Flexible Triangular Ligands 412 23.2.2 Rigid Triangular Ligands 415 23.3 Amino Acid-bridged Dinuclear Titanium(IV) Complexes as Metalloenzyme Mimicry 420 23.4 Conclusions 423 References 423 24 Self-assembly of Dinuclear Helical Metallosupramolecular Coordination Compounds 427 Ulf Kiehne, Jens Bunzen, and Arne Lützen 24.1 Introduction 427 24.2 The Concept of Diastereoselective Self-assembly of Dinuclear Helicates 429 24.3 Synthesis of Building Blocks for the Covalent Assembly of Bis(chelating) Ligands 430 24.3.1 Synthesis of Dissymmetric Elements 430 24.3.2 Synthesis and Resolution of 9,90-Spirobifluorenes 431 24.3.3 Synthesis and Resolution of Tröger.s Base Derivatives 431 24.3.4 Synthesis of 2,20-Bipyridines 432 24.4 Synthesis of Bis(chelating) Ligands and Their Dinuclear Metal Complexes 434 24.4.1 D-Isomannide-based Ligand and Its Complexes 434 24.4.2 9,90-Spirobifluorene-based Ligand and Its Complexes 437 24.4.3 Tröger.s Base Derivatives-based Ligands and Their Complexes 437 24.5 Conclusions 441 References 442 Index 447