title: Computed NMR shielding increments over unsaturated five-membered ring heterocyclic compounds as a measure of aromaticity.
abstract: The GIAO-HF method within Gaussian 03 was used to calculate the isotropic shielding value of the proximal hydrogen of a diatomic hydrogen probe at various distances (2.5 A, 3.0 A and 4.0 A) above the plane of 15 conjugated five-membered ring heterocyclic compounds: pyrrole, furan, thiophene, and phosphole and their 2- and 3-nitrogen analogs. Subtraction of the isotropic shielding value of diatomic hydrogen by itself from each of these isotropic shielding values gave the shielding increment (Deltasigma) for each probe position. Plotting Deltasigma 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 at 2.5 A above the ring center (Deltasigma(2.5)) correlated reasonably well with other established methods of assessing aromaticity, including geometric (HOMA, harmonic oscillator model of aromaticity), energetic (ASE, aromatic stabilization energy), and magnetic (NICS, nucleus-independent chemical shift) criteria.
authors.affiliation: Department of Chemistry and Biochemistry, University of North Carolina Wilmington, 601 South College Road, Wilmington, NC 28403-5932, USA. martinn@uncw.edu
authors.forename: Ned H
authors.initials: NH
authors.lastname: Martin
authors.forename: Jimmy E
authors.initials: JE
authors.lastname: Rowe
authors.forename: Eddie LaReece
authors.initials: EL
authors.lastname: Pittman
mesh_terms: D005663:Furans / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000737:chemistry*; D007093:Imidazoles / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D015394:Molecular Structure; D010080:Oxazoles / Q000737:chemistry; D011720:Pyrazoles / Q000737:chemistry; D011758:Pyrroles / Q000737:chemistry
chemical_list: D005663:Furans; D006571:Heterocyclic Compounds; D007093:Imidazoles; D010080:Oxazoles; D011720:Pyrazoles; D011758:Pyrroles; C031280:pyrazole; C029899:imidazole; C039281:furan