DENSITY-FUNCTIONAL THEORY GIAO STUDIES OF THE C-13, N-15, AND H-1-NMRCHEMICAL-SHIFTS IN AMINOPYRIMIDINES AND AMINOBENZENES - RELATIONSHIPSTO ELECTRON-DENSITIES AND AMINE GROUP ORIENTATIONS

The dependence of the C-13, N-15, and H-1 isotropic NMR chemical shift s on amine substitution of aromatic ring systems are examined both exp erimentally and by DFT/GIAO (density functional theory/gauge including atomic orbitals) methods. There are large, monotonic decreases in the chemical shifts at odd-numbered (ortho and para) pyrimidine ring posi tions which do not occur at the even-numbered (ipso and meta) atoms as amine groups progressively replace hydrogens at the latter positions. This behavior parallels the computed 2p(z) electron densities which f or the pyrimidine series increase monotonically at N1, N3, and C5 but exhibit small changes at the C2, C4, and C6 positions. Identical trend s are noted for the aminobenzenes. The ring atom chemical shifts and 2 p(z) electron densities at ortho and para (but not meta) positions are quite sensitive to the orientations of the amine groups which are pyr amidalized as the result of balance between delocalization with the ri ng and the use of strongly directed sp(3) orbitals at the nitrogen. Th e calculated results show that the barriers to amine group torsional a nd inversion motions are low, but averaging the chemical shifts over t hese appears to be relatively unimportant. Differences between the DFT and Hartree-Fock-based chemical shifts show that electron correlation effects monotonically increase with the number of NH2 substituents.