Charge chemical shift

The degree of charging of 242 is obtained from a simple charge-chemical shift... 

VAMP can be used with Tsar to provide quantum mechanically calculated descriptors for QSAR. Apart from molecular properties such as dipole, quadrupole, and octupole moments, ionization potential, electron affinity, polarizability (calculated as a default in VAMP by a variational method), etc., atomic properties such as Coulson-, Mulliken-, or MEP-derived charges, chemical shifts and atomic dipoles and quadrupoles, VAMP can also calculate surface electrostatic descriptors introduced by Politzer, and is useful for QSARs and QSPRs involving intermolecular interactions. Many of these descriptors can be exported directly into Tsar for analysis by classical regression techniques or artificial neural nets. ... 

A structure with three of the ligands disposed as in the letter Y Partial positive charge Chemical shift (NMR)... 

Figure Bl.11.6. and chemical shifts in phenol, relative to benzene in each case. Note that 5 (H or C) approximately follows 6 (the partial charge at C).

Ab-initio calculations are particularly usefiil for the prediction of chemical shifts of unusual species". In this context unusual species" means chemical entities that are not frequently found in the available large databases of chemical shifts, e.g., charged intermediates of reactions, radicals, and structures containing elements other than H, C, O, N, S, P, halogens, and a few common metals. 

The chemical shifts of in natural abundance have been measured for thiazole and many derivatives (257,258). They are given in Tables 1-37 and T38. These chemical shifts are strongly dependent on the nature of the substituent CNDO/2 calculations have shown (184) that they correlate well with the ((t+tt) net charge of the atom considered. As a consequence, the order of the resonance signals is the same for protons and for carbon atoms. 

NMR spectroscopy is ideal for detecting charged fluorinated intermediates and has been applied to the study of increasingly stable carbocation and carbanion species. Olah [164, 165] has generated stable fluorocarbocations m SbFj/SOjClF at low temperatures The relatively long-lived perfluoro-rerr-butyl anion has been prepared as both the cesium and tris(dimethylamino)sulfonium (TAS) salts by several groups [166, 167, 168], Chemical shifts of fluonnated carbocations and carbanions are listed m Table 23. 

Plot para chemical shift (vertical axis) vs. para atomic charge (horizontal axis). Are the two properties correlated If they are, what is their relationship Does chemical shift increase ( C becomes deshielded) or decrease ( C becomes shielded) with increasing negative charge at carbon ... 

Draw the most important resonance contributors for nitrobenzene (include all of the contributors needed to explain for the variation in electrostatic potential, charge and chemical shift relative to benzene). Do these resonance contributors account for the different behavior of 6meta and 6paia Explain. 

The indoloquinolizidine alkaloid Villagorgin B (360) was isolated from the Gorgonian Villagorgia rubra collected in New Caledonia (Scheme 108). The positive charge of the molecule was deduced from the chemical shifts of the C-6 and C-5 ethylene bridge. However, only one NH group was detectable in NMR in DMSO-Jg (93TL7773). Additional heteroaromatic... 

Equilibrium constants for complex formation (A") have been measured for many donor-acceptor pairs. Donor-acceptor interaction can lead to formation of highly colored charge-transfer complexes and the appearance of new absorption bands in the UV-visible spectrum may be observed. More often spectroscopic evidence for complex formation takes the font) of small chemical shift differences in NMR spectra or shifts in the positions of the UV absorption maxima. In analyzing these systems it is important to take into account that some solvents might also interact with donor or acceptor monomers. 

TABLE 5.3 The Chemical Shift Values, in Parts per Million (ppm) from for the Charged Carbon Atom of Some Carbocations in SO2CIF—SbFs, SOj-FSOaH-SbFft, or SOz-SbFj... 

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