Activating Unreactive Substrates: The Role of Secondary Interactions / Edition 1

Activating Unreactive Substrates: The Role of Secondary Interactions / Edition 1

by Carsten Bolm
     
 

ISBN-10: 3527318232

ISBN-13: 9783527318230

Pub. Date: 03/10/2009

Publisher: Wiley

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

Overview

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.

Product Details

ISBN-13:
9783527318230
Publisher:
Wiley
Publication date:
03/10/2009
Pages:
481
Product dimensions:
6.80(w) x 9.60(h) x 1.20(d)

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

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