Phenyllithium chemical shift

As a consequence of the small quadrupole moment of Li, the quadrupolar interaction in solid state NMR spectra is much smaller for Li than for Li. This has been used to advantage for the determination of the Li chemical shift anisotropy from the Li static solid state powder spectrum of 2,4,6-tris(isopropyl)phenyllithium (see below) . Applying MAS up to 10 kHz, the CSA contributions to the lineshape can be completely ehminated in most Li spectra of organolithium compounds. If the measurement of the quadrupolar... 

In Table 3, the observed C chemical shifts obtained in the solid state are compared to the shifts in solution. It is evident that the agreement between shifts in the solid state and solution is relatively good. The largest discrepancy is observed for the ipio-carbon in the uncomplexed phenyllithium tetramer model and the tetramer in solution measured... 

By the action of phenyllithium, pyridazine is converted to adduct 100 (Table XVI), resulting from nucleophilic attack at position 3.34 The structural assignment is based upon H- and 13C-NMR, starting with pyridazine and its 4,5-dideutero derivative. The site of attachment of the phenyl group is other than that observed with the amide ion in ammonia (C-4). Analysis of the products obtained after hydrolysis and oxidation indicates the presence of nearly 5-6% of 4-phenyIpyridazine. Although this finding implies the formation of a small amount of the isomeric adduct 101, there is no NMR evidence for it. However, both isomeric adducts can be detected when the reaction is carried out in the presence of TMEDA or tetrahydrofuran at a lower temperature. The chemical shift values of adduct 101 are closely similar to those of the amino analog 29. 

The solid-state hexamers (2)—(4) at first appeared to dissolve intact in benzene (94). Cryoscopic rmm measurements over a range of concentrations (0.03-0.09 M, molarity expressed relative to the empirical formula mass) implied n values of 5.9-6.1. Furthermore, their room-temperature 7Li NMR spectra in c/8-toluene each consisted of broad singlets within the narrow chemical shift (6) range of + 0.6 to -0.2 ppm (relative to external phenyllithium in the same solvent). However, variations in temperature and concentration affected the 7Li NMR spectra of (2) and, in particular, of (4) (95). Figure 18a shows these spectra for three d8-toluene solutions of (4) at -100°C. The most concentrated solution has a dominant signal at 8 -+0.7, though five or six other signals (indicated by asterisks) are apparent. On dilution,... 

Figure 12.27 Large paramagnetic contributions to C chemical shifts in phenyllithium and pyridine. Values from...

Figure 4 Principal values and orientation of the principal axes of the ipso-caibon chemical shift tensor in phenyllithium...

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