Lanthanide magnetic resonance spectroscopie

Peters, J.A., Huskens, J., and Raber, D.J. (1996) Lanthanide induced shifts and relaxation rate enhancements. Progress in Nuclear Magnetic Resonance Spectroscopy, 28, 283-350. 

Desreux, J.F. (1980) Nuclear magnetic resonance spectroscopy of lanthanide complexes with a tetraacetic tetraaza macrocycle. Unusual conformation properties. Inorganic Chemistry, 19 (5), 1319—1324. 

J.J. Rh5me, Highlights from the exotic phenomena of lanthanide magnetism 293 B. Bleaney, Magnetic resonance spectroscopy and hyperfine interactions 323... 

Nuclear Magnetic Resonance Spectroscopy.—As noted above, conformational analysis of bicyclo[3.3.1]nonanes is still a topic of considerable interest. A variable-temperature n.m.r. analysis now provides the first case in which the boat-chair-chair-boat equilibrium is directly observed in the amines (17) and (18). In a related case, re-examination of the acetal (19) suggests that the preferred conformation involves a chair carbocyclic ring and a boat heterocyclic ring. This conclusion was made by n.m.r. analysis, using lanthanide shift reagents, by a study of nuclear Overhauser effects, and by measurement of relaxation times of protons. Details have been reported for other 3-azabicyclo[3.3.1]nonanes, and the non-additivity of substituent effects on chemical shifts in 9-thiabicyclo[3.3.1]non-2-enes has been analysed. Both and n.m.r. data have been reported for a series of 9-borabicyclo[3.3.1]non-anes and their pyridine complexes. 

In other important publications, data have been collected and interpreted for a variety of structural types, especially isomers, thereby aiding their identification 196, 215, 369, 419, 460—463, 473, 484). Long-range coupling 283), solvent- 103, 241, 413, 414) and lanthanide-induced shifts 238, 239) and, more recently, nuclear magnetic resonance spectroscopy 151, 362) have also proved of value in the structural assignment of coumarins. 

Glockhart 1976 Lanthanide shift reagents in nuclear magnetic resonance spectroscopy. CRC Critical Reviews in Anal Chem 6 69-130... 

Cockerill AF, Davies GLO, Harden RC and Rackham DM (1973) Lanthanide shift reagents for nuclear magnetic resonance spectroscopy. Chemical Reviews 73 553-588. 

Although nuclear magnetic resonance (NMR) spectroscopy has been used to study a variety of lanthanide based systems like contrast agents for medical imaging applications, only a handful of studies on lanthanide SMMs using NMR have been performed to date. These include the neutral [Ln(Pc)2]°(Ln = Dy or Tb)... 

This volume of the Handbook illustrates the rich variety of topics covered by rare earth science. Three chapters are devoted to the description of solid state compounds skutteru-dites (Chapter 211), rare earth-antimony systems (Chapter 212), and rare earth-manganese perovskites (Chapter 214). Two other reviews deal with solid state properties one contribution includes information on existing thermodynamic data of lanthanide trihalides (Chapter 213) while the other one describes optical properties of rare earth compounds under pressure (Chapter 217). Finally, two chapters focus on solution chemistry. The state of the art in unraveling solution structure of lanthanide-containing coordination compounds by paramagnetic nuclear magnetic resonance is outlined in Chapter 215. The potential of time-resolved, laser-induced emission spectroscopy for the analysis of lanthanide and actinide solutions is presented and critically discussed in Chapter 216. 

Up to about the 1960 s, elemental analysis coupled with absorption spectra and infrared spectra and X-ray crystallography were the primary methods used in the studies of complexes. Later on with the developments in nuclear magnetic resonance (NMR) spectroscopy, especially multinuclear NMR, this technique has been invariably used in the studies of structural features of lanthanide complexes. To illustrate these points some references to literature are herein pointed out. The studies on the rare earth 1,3-diketonates, where 1,3-diketones are acetyl acetone, benzoyl acetone, dibenzoyl methane and 2-thienoyl tri-fluoroacetone totally relied on elemental analysis, UV-Vis and IR spectra to establish the nature of the complexes [89]. The important role played by X-ray crystallography in the elucidation of the structures of lanthanide complexes has been extensively discussed in Chapter 5 and the use of this technique goes as far back as the 1960 s. Nevertheless it continues to play a major role in the studies of lanthanide complexes. 

J. Reuben, in Progress in Nuclear Magnetic Resonance Speetroscopy , Vol. 9, Pt. 1 Lanthanide Shift Reagents m NMR Spectroscopy Principles, Methodology and Applications , Pergamon Press, Oxford, 1973. 

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