The effects of C by N replacement on the hydrogen bonding of malonaldehyde: N-formylformimidic acid, N-(hydroxymethyl)formamide and related compounds
作者： Pablo Sanz , Otilia Mó , Manuel Yáñez , José Elguero
DOI: 10.1039/B815827D
关键词:
摘要: The effects of C by N replacement on the intramolecular hydrogen bond malonaldehyde have been analyzed through use B3LYP/6-311++G(3df,2p)//B3LYP/6-311+G(d,p) calculations. Formylformimidic acid (1) exhibits a IMHB much stronger than that malonaldehyde, reflecting enhancement both intrinsic acidity and basicity HB donor acceptor, when is replaced nitrogen. Similar are observed for N-(aminomethylene) formamide (2), N-(iminomethyl)formimidic (3) N-(aminomethylene)formimidamide (4). corresponding saturated compounds present weaker IMHBs, but this clearly due to characteristics C(1)sigma-skeleton, which forces acceptor not be coplanar away from each other. As matter fact, planar C(s) structures exhibit IMHBs C(1) equilibrium structures. Quite unexpectedly, length in nitrosoformaldehyde oxime (5) slightly fact its conformation, leading an unfavorable orientation with respect acceptor. Again, if symmetry system constrained significant reinforcement observed, ratifying main factor governing strength these sigma-skeleton possible resonance effects.
rsc.org
sci-hub.se 参考文章(42)
George A. Jeffrey, An Introduction to Hydrogen Bonding ,(1997)
Leticia Gonz�lez, Otilia M�, Manuel Y��ez, High‐level ab initio versus DFT calculations on (H2O2)2 and H2O2–H2O complexes as prototypes of multiple hydrogen bond systems Journal of Computational Chemistry. ,vol. 18, pp. 1124- 1135 ,(1997) , 10.1002/(SICI)1096-987X(19970715)18:9<1124::AID-JCC2>3.0.CO;2-T
F Richard, R Bader, Atoms in molecules : a quantum theory Clarendon Press. ,(1990)
Manuel Alcamí, Otilia Mó, Manuel Yáñez, Modeling intrinsic basicities and acidities Journal of Physical Organic Chemistry. ,vol. 15, pp. 174- 186 ,(2002) , 10.1002/POC.467
R. Parthasarathi, V. Subramanian, N. Sathyamurthy, Hydrogen Bonding in Phenol, Water, and Phenol−Water Clusters Journal of Physical Chemistry A. ,vol. 109, pp. 843- 850 ,(2005) , 10.1021/JP046499R
John Frederick Beck, Yirong Mo, How resonance assists hydrogen bonding interactions: an energy decomposition analysis. Journal of Computational Chemistry. ,vol. 28, pp. 455- 466 ,(2007) , 10.1002/JCC.20523
U. Koch, P. L. A. Popelier, CHARACTERIZATION OF C-H-O HYDROGEN-BONDS ON THE BASIS OF THE CHARGE-DENSITY The Journal of Physical Chemistry. ,vol. 99, pp. 9747- 9754 ,(1995) , 10.1021/J100024A016
Charles L. Perrin, Jonathan S. Lau, Hydrogen-bond symmetry in zwitterionic phthalate anions: symmetry breaking by solvation. Journal of the American Chemical Society. ,vol. 128, pp. 11820- 11824 ,(2006) , 10.1021/JA063797O
A. Martín Pendás, M. A. Blanco, E. Francisco, The nature of the hydrogen bond: a synthesis from the interacting quantum atoms picture. Journal of Chemical Physics. ,vol. 125, pp. 184112- 184112 ,(2006) , 10.1063/1.2378807
Axel D. Becke, A New Mixing of Hartree-Fock and Local Density-Functional Theories Journal of Chemical Physics. ,vol. 98, pp. 1372- 1377 ,(1993) , 10.1063/1.464304