Computed NMR shielding increments over benzo-analogs of unsaturated five-membered ring heterocyclic compounds as a measure of aromaticity.

Abstract The GIAO-HF method in Gaussian 03 was used to calculate the isotropic shielding value of the proximal hydrogen of a diatomic hydrogen probe moved in a square grid 2.5 A above the plane of 15 benzo-fused analogs of conjugated five-membered ring heterocyclic compounds: pyrrole, furan, thiophene, and phosphole and their 2- and 3-nitrogen analogs. Subtraction of the calculated isotropic shielding value of diatomic hydrogen from each of these isotropic shielding values gave the shielding increment (Δ σ ) for each probe position. Plotting this value against Cartesian coordinates of the probe position allowed determination of the computed through-space shielding increment surfaces for these compounds. Substantial shielding was observed above the center of each ring, as expected for aromatic compounds. The magnitude of the shielding increment 2.5 A above the heterocyclic ring center correlated reasonably well with the only other published method of assessing aromaticity of these systems ASE (aromatic stabilization energy) and with our calculated NICS (nucleus-independent chemical shift) values, another magnetic criterion. The magnitude of the shielding increment measured over the benzene ring midpoint did not correlate well with other measures of aromaticity, however.