Paul S. Pregosin 
NMR in Organometallic Chemistry [EPUB ebook] 

Preface xi

Abbreviations xiii

1 Introduction 1

References 5

2 Routine Measuring and Relaxation 7

2.1 Getting Started 7

2.2 Relaxation 9

2.2.1 Dipole–Dipole Relaxation 12

2.2.2 Chemical Shift Anisotropy 15

2.2.3 Passing Comments 16

2.2.4 Useful Tips 16

References 17

3 COSY and HMQC 2-D Sequences 19

3.1 Tactics 19

3.2 Cosy 20

3.3 HMQC and HMBC 21

3.3.1 Methods 21

3.3.2 One-Bond 2-D 13C, 1H Correlations 22

3.3.3 One-Bond 2-D 15N, 1H Correlations 25

3.3.4 Two and Three Long-Range Bond 13C, 1H Correlations 26

3.3.5 X, 1H Correlations 31

References 36

4 Overhauser Effects and 2-D NOESY 39

4.1 Background 39

4.2 Assigning Signals via NOEs and General Applications 40

4.3 X, 1H Overhauser Effects 41

4.4 2-d Noesy 43

4.5 Hoesy 50

4.6 Metal Complexes and NOEs. ROESY vs NOESY 51

References 54

5 Diffusion Constants via NMR Measurements 55

References 60

6 Chemical Shifts 63

6.1 1Hnmr 64

6.1.1 Anisotropic Effects 64

6.1.2 Hydrides 67

6.1.3 Molecular H 2 and η2-X-H–M Complexes with X = C, Si, and H 72

6.1.4 σ-Bound Alkyl Groups 73

6.1.5 η2 , η4 -Olefin, and η6 -Arene Proton Chemical Shifts 74

6.1.6 Allyl and Cp Anions 79

6.1.7 Carbene Ligands 83

6.2 Introduction to Heavy Atom NMR 84

6.3 13c 87

6.3.1 σ-Bound Alkyl, Aryl, and Alkynyl Complexes 89

6.3.2 π-Bound Olefin Complexes 99

6.3.3 Acetylene Complexes 109

6.3.4 Allyl and Cp Complexes 111

6.3.5 Carbonyl Complexes 119

6.3.6 Carbenes, Carbynes, and Related Complexes 125

6.3.7 N-Heterocyclic Carbenes (NHCs) 130

6.4 15Nnmr 134

6.5 19Fnmr 146

6.6 31Pnmr 155

6.7 Transition Metals 179

References 196

Further Reading 206

7 Coupling Constants 207

7.1 Background 207

7.2 One-Bond Interactions 208

7.3 A Short 19F Excursion 216

7.4 Applications Involving 1J 219

7.5 1J(H, D) and Molecular Hydrogen Complexes 220

7.6 1J(C, H) in η2-C-H···M Complexes: Agostic Interactions 222

7.7 Remote Agostic Bonds 226

7.8 1J(Si, H) in η2-Si-H···M Complexes 226

7.9 Trans Influence and 1J 230

7.10 Two- and Three-Bond J-Values 238

7.10.1 Routine 1H Coupling Constants 242

7.10.2 Two and Three-Bond 31P Coupling Constants with 1H 246

7.10.3 An Excursion Involving 31P and 13C J-Values 249

7.10.4 Second-Order Effects in 13C Spectra of Bisphosphine Complexes 251

7.10.5 The Geometric Dependence of 2J(L1 -M-L2) 254

7.10.6 2J(31P-m-1H) 255

7.10.7 2J(x, 1H) 256

7.10.8 2J(31P, 31P) 258

7.10.9 2J(31P, 13C) 264

7.10.10 2J(31P, 19F) 266

7.10.10.1 2J(31P, x) 267

References 273

Further Reading 277

8 Dynamics 279

8.1 Variable Temperature 280

8.2 Line Shape Analysis 284

8.3 Magnetization Transfer 291

8.4 Two-Dimensional NMR and Chemical Exchange 296

References 308

9 Preface to the Problems 311

10 Organometallic Introduction 313

10.1 Oxidative Addition 313

10.2 Migratory Insertion (or Intramolecular Nucleophilic Attack) 314

10.3 External Nucleophilic Attack 314

10.4 Beta-Hydrogen Elimination 315

10.5 Reductive Elimination 315

10.6 Synthesis of Transition Metal–Hydride Complexes 316

10.7 Synthesis of Transition Metal Alkyl Complexes 316

10.8 Synthesis of Transition Metal Carbonyl Complexes 317

10.9 Synthesis of Transition Metal Olefin Complexes 317

10.10 Synthesis of Transition Metal Carbene Complexes 318

11 NMR Problems 319

11.1 Three Sample Problems 319

11.2 NMR Problems 323

12 Solutions to the Problems and Comments 361

Index 389

Paul S. Pregosin received his Ph. D. at the City University of New York. He then carried out postdoctoral research at Queen Mary College, University of London (1970 – 1971), and at the University of Delaware (1971 – 1973). In 1973, he moved to Swiss Federal Institute of Technology in Zurich, Switzerland, where he became Professor of Inorganic Chemistry in 1987. He has also received the Werner Prize
for his work on NMR-spectroscopic studies of transition metal complexes.