NMR in Organometallic Chemistry

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 Prizefor his work on NMR-spectroscopic studies of transition metal complexes.

“However, it certainly conveys its author’s undoubted enthusiasm, and most organometallic and coordination chemists will find it well worth their while to dip into it.”  (Applied Organometal.Chemistry, 1 June 2013)

• Preface xiAbbreviations xiii1 Introduction 1References 52 Routine Measuring and Relaxation 72.1 Getting Started 72.2 Relaxation 92.2.1 Dipole–Dipole Relaxation 122.2.2 Chemical Shift Anisotropy 152.2.3 Passing Comments 162.2.4 Useful Tips 16References 173 COSY and HMQC 2-D Sequences 193.1 Tactics 193.2 Cosy 203.3 HMQC and HMBC 213.3.1 Methods 213.3.2 One-Bond 2-D 13C, 1H Correlations 223.3.3 One-Bond 2-D 15N, 1H Correlations 253.3.4 Two and Three Long-Range Bond 13C, 1H Correlations 263.3.5 X, 1H Correlations 31References 364 Overhauser Effects and 2-D NOESY 394.1 Background 394.2 Assigning Signals via NOEs and General Applications 404.3 X, 1H Overhauser Effects 414.4 2-d Noesy 434.5 Hoesy 504.6 Metal Complexes and NOEs. ROESY vs NOESY 51References 545 Diffusion Constants via NMR Measurements 55References 606 Chemical Shifts 636.1 1Hnmr 646.1.1 Anisotropic Effects 646.1.2 Hydrides 676.1.3 Molecular H 2 and η2-X-H–M Complexes with X = C, Si, and H 726.1.4 σ-Bound Alkyl Groups 736.1.5 η2 , η4 -Olefin, and η6 -Arene Proton Chemical Shifts 746.1.6 Allyl and Cp Anions 796.1.7 Carbene Ligands 836.2 Introduction to Heavy Atom NMR 846.3 13c 876.3.1 σ-Bound Alkyl, Aryl, and Alkynyl Complexes 896.3.2 π-Bound Olefin Complexes 996.3.3 Acetylene Complexes 1096.3.4 Allyl and Cp Complexes 1116.3.5 Carbonyl Complexes 1196.3.6 Carbenes, Carbynes, and Related Complexes 1256.3.7 N-Heterocyclic Carbenes (NHCs) 1306.4 15Nnmr 1346.5 19Fnmr 1466.6 31Pnmr 1556.7 Transition Metals 179References 196Further Reading 2067 Coupling Constants 2077.1 Background 2077.2 One-Bond Interactions 2087.3 A Short 19F Excursion 2167.4 Applications Involving 1J 2197.5 1J(H,D) and Molecular Hydrogen Complexes 2207.6 1J(C,H) in η2-C-H···M Complexes: Agostic Interactions 2227.7 Remote Agostic Bonds 2267.8 1J(Si,H) in η2-Si-H···M Complexes 2267.9 Trans Influence and 1J 2307.10 Two- and Three-Bond J-Values 2387.10.1 Routine 1H Coupling Constants 2427.10.2 Two and Three-Bond 31P Coupling Constants with 1H 2467.10.3 An Excursion Involving 31P and 13C J-Values 2497.10.4 Second-Order Effects in 13C Spectra of Bisphosphine Complexes 2517.10.5 The Geometric Dependence of 2J(L1 -M-L2) 2547.10.6 2J(31P-m-1H) 2557.10.7 2J(x, 1H) 2567.10.8 2J(31P, 31P) 2587.10.9 2J(31P, 13C) 2647.10.10 2J(31P, 19F) 2667.10.10.1 2J(31P,x) 267References 273Further Reading 2778 Dynamics 2798.1 Variable Temperature 2808.2 Line Shape Analysis 2848.3 Magnetization Transfer 2918.4 Two-Dimensional NMR and Chemical Exchange 296References 3089 Preface to the Problems 31110 Organometallic Introduction 31310.1 Oxidative Addition 31310.2 Migratory Insertion (or Intramolecular Nucleophilic Attack) 31410.3 External Nucleophilic Attack 31410.4 Beta-Hydrogen Elimination 31510.5 Reductive Elimination 31510.6 Synthesis of Transition Metal–Hydride Complexes 31610.7 Synthesis of Transition Metal Alkyl Complexes 31610.8 Synthesis of Transition Metal Carbonyl Complexes 31710.9 Synthesis of Transition Metal Olefin Complexes 31710.10 Synthesis of Transition Metal Carbene Complexes 31811 NMR Problems 31911.1 Three Sample Problems 31911.2 NMR Problems 32312 Solutions to the Problems and Comments 361Index 389