Theoretical study of bifurcated hydrogen bonding effects on the 1J(N,H), 1hJ(N,H), 2hJ(N,N) couplings and 1H, 15N shieldings in model pyrroles.

According to the density functional theory calculations, the X...H...N (X=N, O) intramolecular bifurcated (three-centered) hydrogen bond with one hydrogen donor and two hydrogen acceptors causes a significant decrease of the (1h)J(N,H) and (2h)J(N,N) coupling constants across the N-H...N hydrogen bond and an increase of the (1)J(N,H) coupling constant across the N-H covalent bond in the 2,5-disubstituted pyrroles. This occurs due to a weakening of the N-H...N hydrogen bridge resulting in a lengthening of the N...H distance and a decrease of the hydrogen bond angle at the bifurcated hydrogen bond formation. The gauge-independent atomic orbital calculations of the shielding constants suggest that a weakening of the N-H...N hydrogen bridge in case of the three-centered hydrogen bond yields a shielding of the bridge proton and deshielding of the acceptor nitrogen atom. The atoms-in-molecules analysis shows that an attenuation of the (1h)J(N,H) and (2h)J(N,N) couplings in the compounds with bifurcated hydrogen bond is connected with a decrease of the electron density rho(H...N) at the hydrogen bond critical point and Laplacian of this electron density nabla(2)rho(H...N). The natural bond orbital analysis suggests that the additional N-H...X interaction partly inhibits the charge transfer from the nitrogen lone pair to the sigma*(N-H) antibonding orbital across hydrogen bond weakening of the (1h)J(N,H) and (2h)J(N,N) trans-hydrogen bond couplings through Fermi-contact mechanism. An increase of the nitrogen s-character percentage of the N-H bond in consequence of the bifurcated hydrogen bonding leads to an increase of the (1)J(N,H) coupling constant across the N-H covalent bond and deshielding of the hydrogen donor nitrogen atom. Copyright 2010 John Wiley & Sons, Ltd.