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Full Description
The first and ultimate guide for anyone working in transition organometallic chemistry and related fields, providing the background and
practical guidance on how to efficiently work with routine research problems in NMR.
The book adopts a problem-solving approach with many examples taken from recent literature to show readers how to interpret the data.
Perfect for PhD students, postdocs and other newcomers in organometallic and inorganic chemistry, as well as for organic chemists
involved in transition metal catalysis.
Contents
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
