Landmarks in organo-transition metal chemistry: a personal view

Helmut Werner038709847X, 9780387098470, 0387098488, 9780387098487

Since the discovery of ferrocene and the sandwich-type complexes, the development of organometallic chemistry took its course like an avalanche and became one of the scientific success stories of the second half of the twentieth century. Based on this development, the traditional boundaries between inorganic and organic chemistry gradually disappeared and a rebirth of the nowadays highly important field of homogeneous catalysis occurred. It is fair to say that despite the fact that the key discovery, which sparked it all off, was made more than 50 years ago, organometallic chemistry remains a young and lively discipline.

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Table of contents :
Landmarks in Organo-Transition Metal Chemistry……Page 1
Foreword……Page 6
Series Preface……Page 7
Preface……Page 9
Acknowledgments……Page 11
Contents……Page 12
List of Abbreviations……Page 16
Synopsis……Page 17
Prologue……Page 18
References……Page 24
2.1 The Years at Home……Page 25
2.2 The First Move: From Mühlhausen to Jena……Page 35
2.3 The Second Move: From Jena to Munich……Page 40
2.4 The First Years at München……Page 42
2.5 From München to Pasadena and Back……Page 47
2.6 Crossing the Border: The Years at Zürich……Page 57
2.7 Back to Germany……Page 66
2.7.1 Biographies……Page 80
3.1 The Beginnings of Organometallic Chemistry……Page 84
3.2 Wilhelm Christoph Zeise and the First Transition Metal bpi-Complex……Page 85
3.3 Edward Frankland’s Pioneering Studies……Page 86
3.4 Victor Grignard: The Father of ‘‘Organometallics for Organic Synthesis’’……Page 89
3.5 Paul Schützenberger and Ludwig Mond: The First Metal Carbonyls……Page 90
3.5.1 Biographies……Page 93
References……Page 98
4.1 A Class of ‘‘Peculiar Compounds’’……Page 100
4.2 The Giant Work of Walter Hieber……Page 104
4.3 Hieber and his Followers……Page 108
4.4 Surprisingly Stable: Multiply Charged Carbonyl Metallate Anions……Page 113
4.5 Metal Carbonyl Cations: Not Incapable of Existence……Page 115
4.6 Highly Labile Metal Carbonyls……Page 117
4.7 The Exiting Chemistry of Metal Carbonyl Clusters……Page 120
4.8 Otto Roelen and Walter Reppe: Industrial Applications of Metal Carbonyls……Page 125
Biographies……Page 129
References……Page 134
5.1 The Early Days: Ferrocene……Page 143
5.2 The Rivalry of Fischer and Wilkinson……Page 149
5.3 Fischer’s Star: Bis(benzene)chromium……Page 150
5.4 Hein’s ‘‘Polyphenylchromium Compounds’’……Page 152
5.5 Zeiss and Tsutsui: Hein’s Work Revisited……Page 154
5.6 Wilkinson’s Next Steps……Page 159
5.7 From Sandwich Complexes to Organometallic Dendrimers……Page 160
5.8 The Taming of Cyclobutadiene: A Case of Theory before Experiment……Page 164
5.9 The Smaller and Larger Ring Brothers of Ferrocene……Page 166
5.10 Sandwiches with P5 and Heterocycles as Ring Ligands……Page 168
5.11 Two Highlights from the 21st Century……Page 171
5.12 Brintzinger’s Sandwich-Type Catalysts……Page 173
5.13 Woodward and the Nobel Prize……Page 175
5.14.1 Biographies……Page 177
References……Page 183
6.1 The Breakthrough: [Ni2(C5H5)3]+……Page 191
6.2 The Iron and Ruthenium Counterparts……Page 196
6.3 Arene-bridged Triple-Decker Sandwiches……Page 199
6.4 ‘‘Big Macs’’ with Bridging P5, P6 and Heterocycles as Ligands……Page 200
6.5 Tetra-, Penta- and Hexa-Decker Sandwich Complexes……Page 203
References……Page 205
7.1 From 1827 to the 1930s: In the Footsteps of Zeise……Page 209
7.2 Reihlen’s Strange Butadiene Iron Tricarbonyl……Page 213
7.3 Michael Dewar’s ‘‘Landmark Contribution’’……Page 214
7.4 The Dewar-Chatt-Duncanson Model……Page 216
7.5 An Exciting Branch: Mono- and Oligoolefin Metal Carbonyls……Page 218
7.6 Schrauzer’s Early Studies on Homoleptic Olefin Nickel(0) Complexes……Page 222
7.7 Wilke’s Masterpieces and the ‘‘Naked Nickel’’……Page 223
7.8 Stone and the Family of Olefin Palladium(0) and Platinum(0) Compounds……Page 228
7.9 Timms’, Fischer’s and Green’s Distinctive Shares……Page 230
7.10 A Recent Milestone: Jonas’ Olefin Analogues of Hieber’s Metal Carbonylates……Page 233
7.11.1 Biographies……Page 235
References……Page 242
8.1 The Search for Divalent Carbon Compounds……Page 249
8.2 From Wanzlick’s and Öfele’s Work to Arduengo’s Carbenes……Page 251
8.3 The Breakthrough: Fischer’s Metal Carbenes……Page 252
8.4 The Next Highlight: Fischer’s Metal Carbynes……Page 255
8.5 Öfele’s, Casey’s and Chatt’s Routes to Metal Carbenes……Page 256
8.6 Lappert’s Seminal Work on Bis(amino)carbene Complexes……Page 258
8.7 A Big Step: Schrock’s Metal Carbenes and Carbynes……Page 261
8.8 Fischer and His Followers……Page 267
8.9 Using the Isolobal Analogy: Metal Complexes with Bridging Carbenes and Carbynes……Page 270
8.10 The Seemingly Existing CCl2 and Its Generation at Transition Metal Centers……Page 273
8.12 The First and Second Generation of Grubbs’ Ruthenium Carbenes……Page 277
8.13 From Metal Carbenes to Open-Shell Metal Carbyne and Carbido Complexes……Page 282
8.14 The Dötz Reaction and the Use of Metal Carbenes for Organic Synthesis……Page 285
8.15 Olefin Metathesis: A Landmark in Applied Organometallic Chemistry……Page 286
8.16 An Extension: Metal Complexes with Unsaturated Carbenes……Page 288
References……Page 298
9.1 The Extensions of Frankland’s Pioneering Work……Page 311
9.2 Heteroleptic Complexes with Metal-Alkyl and Metal-Aryl Bonds……Page 313
9.3 Chatt and His Contemporaries……Page 314
9.4 Lappert, Wilkinson and the Isolation of Stable Metal Alkyls und Aryls……Page 318
9.5 An Apparent Conflict: Metal Alkyls and Aryls Containing sigma- and pi-Donor Ligands……Page 324
9.6 Binary Metal Alkyls with MM Multiple Bonds……Page 328
9.7 The Recent Highlight: Power’s RCrCrR and the Fivefold CrCr Bonding……Page 329
9.8 Novel Perspectives: Metal Alkyls and Aryls Formed by CH and CC Bond Activation……Page 331
9.9 Metal Alkyls and Aryls in Catalysis……Page 338
References……Page 339
Epilogue……Page 350
Index……Page 353