Fundamentals of Porphyrin Chemistry

Volume 1

List of Contributors xiii

1 An Introduction to Porphyrins for the Twenty-First Century 1
Penelope J. Brothers and Mathias O. Senge

1.1 Why Porphyrins? 1

1.2 The Natural World of Porphyrins 3

1.3 Brief History of Porphyrins 4

1.4 Practical Applications 5

1.5 Porphyrins for the Twenty-First Century 7

2 It's All in the Name 9
Mathias O. Senge

2.1 Basic Structure and Nomenclature of Porphyrins 9

2.2 General Classes of Porphyrin Systems 11

2.3 Naturally Occurring Porphyrins 15

2.4 Special Aspects of Porphyrin Nomenclature 24

2.5 Porphyrin Stenography 30

3 Organic Synthesis and Reactivity of Porphyrins 37
Mathias O. Senge and Alina Meindl

3.1 Introduction 37

3.2 Synthesis of meso-Substituted Porphyrins from Pyrrole Building Blocks 39

3.3 Synthesis of ¿-Substituted Porphyrins from Pyrrole Building Blocks 52

3.4 Total Synthesis of Other Porphyrin(oid)s 57

3.5 Reactivity of Porphyrins 66

3.6 Transition-Metal-Catalyzed Reactions at the Porphyrin Macrocycle 79

3.7 Peripheral Functionalization 91

3.8 Examples of Classic and Contemporary Target Systems 103

4 Coordination Chemistry 141
Penelope J. Brothers and Abhik Ghosh

4.1 Introduction 142

4.2 Overview of the Coordination Chemistry of Porphyrin and its Analogues 143

4.3 Metallation, Demetallation, and Characterization 152

4.4 Main Group Elements 158

4.5 Transition Metals 170

4.6 Lanthanides and Actinides 197

4.7 Organometallic Porphyrin Complexes 204

5 Phthalocyanines and Porphyrazines 241
Ümit Isci and Fabienne Dumoulin

5.1 Phthalocyanines and Porphyrazines: Structures and Syntheses of Peculiar Members of the Porphyrin Family 241

5.2 Synthetic Methods and Strategies 247

5.3 Preparation and Characterization of Precursors 250

5.4 Formation of Macrocycles with Asymmetric Substitution Patterns 262

5.5 Lanthanide Double- and Multi-Decker Derivatives 272

5.6 Other Double- and Multi-Decker Derivatives 276

5.7 Reactions on Phthalocyanines and Porphyrazines 278

5.8 Conclusion 289

6 Oxidation and Reduction of Porphyrins 303
Christian Brückner and Nisansala Hewage

6.1 Introduction: Scope and Limits of This Chapter 303

6.2 Reductions of Porphyrins 304

6.3 Oxidations of Porphyrins 311

6.4 Metal-Centered and Resonance-Stabilized ¿-System Redox Events 330

7 Corroles and Contracted Porphyrins 349
Daniel T. Gryko and Mariusz Tasior

7.1 Introduction 349

7.2 Corroles 349

7.3 Isocorroles 368

7.4 N-Confused Corroles 369

7.5 Heteroanalogues of Corroles 369

7.6 Norcorroles 373

7.7 Outlook 374

8 Heteroporphyrins and Carbaporphyrins 385
Timothy D. Lash

8.1 Introduction 385

8.2 Mono- and Diheteroporphyrins (O, S, Se, Te) 386

8.3 Tetraoxa-, Tetrathia-, and Tetraselenaporphyrin Dications 397

8.4 Phosphaporphyrins 400

8.5 Carbaporphyrinoid Systems 402

8.6 True Carbaporphyrins 405

8.7 Azuliporphyrins 416

8.8 Neo-Confused Porphyrins 427

8.9 Benziporphyrins 427

8.10 Miscellaneous Carbaporphyrinoid Systems 434

8.11 Dicarbaporphyrinoids 439

8.12 Tetracarbaporphyrinoids 445

8.13 Related Porphyrin Analogues 447

8.14 Conclusions 448

9 Expanded Porphyrins 453
Atsuhiro Osuka and Takayuki Tanaka

9.1 Historical Background 453

9.2 One-Pot Synthesis of Expanded Porphyrins 455

9.3 Size-Selective Syntheses of Expanded Porphyrins 461

9.4 Möbius Aromatic Expanded Porphyrins 466

9.5 Giant Expanded Porphyrins 471

References 473

Volume 2

List of Contributors xiii

10 Fundamentals of Porphyrin and Metalloporphyrin Stereochemistry 479
W. Robert Scheidt

11 Porphyrins: Electronic Structure and Ultraviolet/Visible Absorption Spectroscopy 505
M. Cather Simpson and Nina I. Novikova

12 Photoinduced Electron and Energy Transfer 587
Eugeny A. Ermilov and Beate Röder

13 NMR Spectroscopy of Porphyrins 611
Craig J. Medforth

14 Spin States in Iron Porphyrins 631
Mikio Nakamura

15 Electrochemical Properties of Porphyrin-Type Complexes 661
Tebello Nyokong

16 Heme Proteins -- Structure and Function 709
Sk Amanullah, Chandradeep Ghosh, Somdatta Ghosh Dey and Abhishek Dey

17 Chlorophylls 743
Hitoshi Tamiaki

18 Vitamin B12 and Cofactor F430 777
Bernhard Kräutler and Bernhard M. Jaun

Index 815