Landmarks in Organo-Transition Metal Chemistry (eBook)

As an undergraduate student, Helmut Werner worked for his Diploma Thesis with Franz Hein, one of the giants of coordination chemistry in Germany from 1920 to 1960, and obtained his Ph. D. in the laboratory of Ernst Otto Fischer, one of the great heros of organo-transition metal chemistry in the latter half of the twentieth century. He prepared the first borazine-metal complexes, isolated the chemical Big Mac, promoted the concept of metal basicity, investigated the chemistry of metalla-cumulenes and, most recently, discovered a new bonding mode for tertiary phosphines, arsines and stibines. He held academic positions at the Technical University of Munich, the University of Zürich and the University of Würzburg, and from 1990-2001 was the Chairman of an Interdisciplinary Research Unit in organometallic chemistry.

Foreword 7
Series Preface 8
Preface 10
Acknowledgments 12
Contents 13
List of Abbreviations 17
Synopsis 18
Prologue 19
References 25
Biographical Sketch 26
2.1 The Years at Home 26
2.2 The First Move: From Mühlhausen to Jena 36
2.3 The Second Move: From Jena to Munich 41
2.4 The First Years at München 43
2.5 From München to Pasadena and Back 48
2.6 Crossing the Border: The Years at Zürich 58
2.7 Back to Germany 67
2.7.1 Biographies 81
The Nineteenth Century: A Sequence of Accidental Discoveries 85
3.1 The Beginnings of Organometallic Chemistry 85
3.2 Wilhelm Christoph Zeise and the First Transition Metal bpi-Complex 86
3.3 Edward Frankland’s Pioneering Studies 87
3.4 Victor Grignard: The Father of ‘‘Organometallics for Organic Synthesis’’ 90
3.5 Paul Schützenberger and Ludwig Mond: The First Metal Carbonyls 91
3.5.1 Biographies 94
References 99
Transition Metal Carbonyls: From Small Molecules to Giant Clusters 101
4.1 A Class of ‘‘Peculiar Compounds’’ 101
4.2 The Giant Work of Walter Hieber 105
4.3 Hieber and his Followers 109
4.4 Surprisingly Stable: Multiply Charged Carbonyl Metallate Anions 114
4.5 Metal Carbonyl Cations: Not Incapable of Existence 116
4.6 Highly Labile Metal Carbonyls 118
4.7 The Exiting Chemistry of Metal Carbonyl Clusters 121
4.8 Otto Roelen and Walter Reppe: Industrial Applications of Metal Carbonyls 126
Biographies 130
References 135
A Scientific Revolution: The Discovery of the Sandwich Complexes 144
5.1 The Early Days: Ferrocene 144
5.2 The Rivalry of Fischer and Wilkinson 150
5.3 Fischer’s Star: Bis(benzene)chromium 151
5.4 Hein’s ‘‘Polyphenylchromium Compounds’’ 153
5.5 Zeiss and Tsutsui: Hein’s Work Revisited 155
5.6 Wilkinson’s Next Steps 160
5.7 From Sandwich Complexes to Organometallic Dendrimers 161
5.8 The Taming of Cyclobutadiene: A Case of Theory before Experiment 165
5.9 The Smaller and Larger Ring Brothers of Ferrocene 167
5.10 Sandwiches with P5 and Heterocycles as Ring Ligands 169
5.11 Two Highlights from the 21st Century 172
5.12 Brintzinger’s Sandwich-Type Catalysts 174
5.13 Woodward and the Nobel Prize 176
Biographies 178
References 184
One Deck More: The Chemical ‘‘Big Mac’’ 192
6.1 The Breakthrough: [Ni2(C5H5)3]+ 192
6.2 The Iron and Ruthenium Counterparts 197
6.3 Arene-bridged Triple-Decker Sandwiches 200
6.4 ‘‘Big Macs’’ with Bridging P5, P6 and Heterocycles as Ligands 201
6.5 Tetra-, Penta- and Hexa-Decker Sandwich Complexes 204
Notes 206
References 206
The Binding of Ethene and Its Congeners: Prototypical Metal pi-Complexes 210
7.1 From 1827 to the 1930s: In the Footsteps of Zeise 210
7.2 Reihlen’s Strange Butadiene Iron Tricarbonyl 214
7.3 Michael Dewar’s ‘‘Landmark Contribution’’ 215
7.4 The Dewar-Chatt-Duncanson Model 217
7.5 An Exciting Branch: Mono- and Oligoolefin Metal Carbonyls 219
7.6 Schrauzer’s Early Studies on Homoleptic Olefin Nickel(0) Complexes 223
7.7 Wilke’s Masterpieces and the ‘‘Naked Nickel’’ 224
7.8 Stone and the Family of Olefin Palladium(0) and Platinum(0) Compounds 229
7.9 Timms’, Fischer’s and Green’s Distinctive Shares 231
7.10 A Recent Milestone: Jonas’ Olefin Analogues of Hieber’s Metal Carbonylates 234
Biographies 236
References 243
Metal Carbenes and Carbynes: The Taming of ‘‘Non-existing’’ Molecules 250
8.1 The Search for Divalent Carbon Compounds 250
8.2 From Wanzlick’s and Öfele’s Work to Arduengo’s Carbenes 252
8.3 The Breakthrough: Fischer’s Metal Carbenes 253
8.4 The Next Highlight: Fischer’s Metal Carbynes 256
8.5 Öfele’s, Casey’s and Chatt’s Routes to Metal Carbenes 257
8.6 Lappert’s Seminal Work on Bis(amino)carbene Complexes 259
8.7 A Big Step: Schrock’s Metal Carbenes and Carbynes 262
8.8 Fischer and His Followers 268
8.9 Using the Isolobal Analogy: Metal Complexes with Bridging Carbenes and Carbynes 271
8.10 The Seemingly Existing CCl2 and Its Generation at Transition Metal Centers 274
8.11 The Congeners of Metal Carbynes with ME Triple Bonds 278
8.12 The First and Second Generation of Grubbs’ Ruthenium Carbenes 278
8.13 From Metal Carbenes to Open-Shell Metal Carbyne and Carbido Complexes 283
8.14 The Dötz Reaction and the Use of Metal Carbenes for Organic Synthesis 286
8.15 Olefin Metathesis: A Landmark in Applied Organometallic Chemistry 287
8.16 An Extension: Metal Complexes with Unsaturated Carbenes 289
References 299
Metal Alkyls and Metal Aryls: The ‘‘True’’ Transition Organometallics 312
9.1 The Extensions of Frankland’s Pioneering Work 312
9.2 Heteroleptic Complexes with Metal-Alkyl and Metal-Aryl Bonds 314
9.3 Chatt and His Contemporaries 315
9.4 Lappert, Wilkinson and the Isolation of Stable Metal Alkyls und Aryls 319
9.5 An Apparent Conflict: Metal Alkyls and Aryls Containing sigma- and pi-Donor Ligands 325
9.6 Binary Metal Alkyls with MM Multiple Bonds 329
9.7 The Recent Highlight: Power’s RCrCrR and the Fivefold CrCr Bonding 330
9.8 Novel Perspectives: Metal Alkyls and Aryls Formed by CH and CC Bond Activation 332
9.9 Metal Alkyls and Aryls in Catalysis 339
References 340
Epilogue 351
Index 354