title: Comparative analysis of hydrogen bonding with participation of the nitrogen, oxygen and sulfur atoms in the 2(2'-heteroaryl)pyrroles and their trifluoroacetyl derivatives based on the 1H, 13C, 15N spectroscopy and DFT calculations.
abstract: The N-H...X (X = N,O,S) intramolecular hydrogen bond in the series of 2(2'-heteroaryl)pyrroles and their trifluoroacetyl derivatives is examined by the (1)H, (13)C, (15)N spectroscopy and density functional theory (DFT) calculations. The influence of the hydrogen bond on coupling and shielding constants is considered. It is shown that the N-H...N intramolecular hydrogen bond causes a larger increase in the absolute size of the (1)J(N,H) coupling constant and a larger deshielding of the bridge proton than the N-H...O hydrogen bond. The effect of the N-H...S interaction on the (1)J(N,H) coupling constant and the shielding of the bridge proton is small. The NMR parameter changes in the series of the 2(2'-heteroaryl)pyrroles due to N-H...X hydrogen bond and the series of the 1-vinyl-2-(2'-heteroaryl)-pyrroles due to C-H...X hydrogen bond have the same order. The proximity of the nitrogen, oxygen or sulfur lone pair to the F...H hydrogen bridge quenches the trans-hydrogen bond spin-spin couplings (1h)J(F,H-1) and (2h)J(F,N).
authors.affiliation: Institute of Chemistry, Favorsky St 1, 664033 Irkutsk, Russia. sasha@irioch.irk.ru
authors.forename: Andrei V
authors.initials: AV
authors.lastname: Afonin
authors.forename: Alexander V
authors.initials: AV
authors.lastname: Vashchenko
authors.forename: Igor A
authors.initials: IA
authors.lastname: Ushakov
authors.forename: Nadezhda V
authors.initials: NV
authors.lastname: Zorina
authors.forename: Elena Yu
authors.initials: EY
authors.lastname: Schmidt