Bond magnetic anisotropy

Figure 1 The principal sources of structural data are the NOEs, which give information on the spatial proximity d of protons coupling constants, which give information on dihedral angles < i and residual dipolar couplings, which give information on the relative orientation 0 of a bond vector with respect to the molecule (to the magnetic anisotropy tensor or an alignment tensor). Protons are shown as spheres. The dashed line indicates a coordinate system rigidly attached to the molecule.

In Tabled theoretical magnetic anisotropies AK for selected molecules, calculated assuming the bond lengths shown in Fig. 5, are listed (in units of d.Kbenzene) d Compared with the experimental exaltations reported by Dauben et a/. . Theoretical values are in good agreement... 

Pi-complexing is most commonly used to rationalize effects observed in aromatic solvents. The most frequent evidence cited is magnetic anisotropy effects on chemical shifts in the solute molecule. As was the case for hydrogen bonding no quantitative correlations with substantive parameters such as ultraviolet spectral shifts have been attempted. 

Direct application of Ax for the quantitative evaluation of aromaticity is, however, not practicable since its magnitude is not determined by ring currents only. Quite substantial effects may be played by a local contribution by the 7r-bond anisotropy and the anisotropy of CC and CH (r-bond magnetic susceptibilities as well as by the anisotropy due to local paramagnetic currents (for more detail, see, e.g., 66MI1). 

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