Nuclear Overhauser enhancement negative

In decoupling the methyl protons, the NOE difference spectrum shows a nuclear Overhauser enhancement on the cyclopropane proton at = 1.60 and on the terminal vinyl proton with trans coupling at <5// = 5.05 and, because of the geminal coupling, a negative NOE on the other terminal proton at Sh= 4.87. This confirms the trans configuration G. In the cis isomer H no NOE would be expected for the cyclopropane proton, but one would be expected for the alkenyl-// in the a-position indicated by arrows in H. 

The most convenient technique used to study organotin(IV) derivatives in solution and in solid state is Sn NMR spectroscopy. The Sn nucleus has a spin of 1 /2 and a natural abundance of 8.7% looking only at the isotopic abundance, it is about 25.5 times more sensitive than The isotope Sn is slightly less sensitive (natural abundance 7.7%) but it has not been used as much. Both nuclei have negative gyromagnetic ratios, and, as a consequence, the nuclear Overhauser enhancements are negative. Some examples of the applications of this method are mentioned later, in different sections. 

The latter, in contrast to nuclear Overhauser enhancement and exchange spectroscopy (NOESY), always feature positive NOEs (negative cross-peaks with respect to diagonal), eliminating known problems of NOEs vanishing or spin diffusion, depending on correlation time, when high field spectrometers are used for measurements of medium-size compounds. 

Si NMR studies of solutions are difficult because of the long spin-lattice relaxation times of the nucleus and its negative nuclear Overhauser enhancement. The 29Si-1H dipole-dipole relaxation is inefficient because in most compounds the intemuclear distance is large. Fortunately, the problem of relaxation can often be overcome by resorting to cross-polarization (see Section II,E). 

For Rexco branched/cyclics, gating of the H-noise decoupling (so that it is applied only during signal acquisition) in order that nuclear Overhauser enhancement (n.O.e.) is suppressed causes the intensities of the methylene (29.85 p.p.m.) to decrease relative to that of the methyl (1. 15 p.p.m.). Presumably different relaxation mechanisms predominate in the two cases (j U) for the methylene group, relaxation is mainly dipolar, with positive Overhauser enhancement, whereas the methyl group may relax by spin-rotation with negative Overhauser enhancement. 

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