Pregosin P.S. NMR in Organometallic Chemistry. - Weinheim: Wiley-VCH, 2012. - xiv, 392 p. - Ind.: p.389-392. - ISBN 978-3-527-33013-3  Место хранения:   024 | Институт неорганической химии им. А.В.Николаева CO РАН | Новосибирск

Оглавление / 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 13С,1Н Correlations .................... 22 3.3.3 One-Bond 2-D 15N,1H Correlations ................ 25 3.3.4 Two and Three Long-Range Bond 13С?Н 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 1H NMR ................................................. 64 6.1.1 Anisotropic Effects ............................. 64 6.1.2 Hydrides ........................................ 67 6.1.3 Molecular H2 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 15N NMR ............................................... 134 6.5 19F NMR ............................................... 146 6.6 31P NMR ............................................... 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 Geometrie 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