Grabowski Sławomir Janusz, Małecka Magdalena
Department of Crystallography and Crystal Chemistry, University of Łódź, Pomorska 149/153, 90 236 Łódź, Poland.
J Phys Chem A. 2006 Oct 26;110(42):11847-54. doi: 10.1021/jp064997p.
Intramolecular N-H...O hydrogen bonds in 3-(aminomethylene)pyran-2,4-dione and its simple derivatives (F, Li, and BeH substituents) were analyzed theoretically. The systems were optimized at the B3LYP/6-311++G(d,p) level of approximation. For some fluorine derivatives the corresponding tautomers with O-H...N intramolecular H-bonds were investigated, and for such pairs of tautomers, the calculations on transition states of the N-H...O <--> N...H-O proton-transfer reaction were carried out. The geometrical and energetic parameters for these species were characterized. The topological parameters derived from Bader theory were also analyzed; these are characteristics of H-bond critical points and also of ring critical points. Besides N-H...O and O-H...N intramolecular hydrogen bonds, there are the other intramolecular interactions, mostly ionic such as Be(+delta)...(-delta)O, Li(+delta)...(-delta)O, and Li(+delta)...(-delta)F. The F...O interactions also exist for some of species investigated. They may be classified as energetically stabilizing ones since the corresponding bond paths and critical points exist. The numerous correlations and dependencies between geometrical, topological, and energetic parameters were detected and described.
对3-(氨基亚甲基)吡喃-2,4-二酮及其简单衍生物（氟、锂和氢化铍取代基）中的分子内N-H...O氢键进行了理论分析。这些体系在B3LYP/6-311++G(d,p)近似水平上进行了优化。对于一些氟衍生物，研究了具有O-H...N分子内氢键的相应互变异构体，并且对于这样的互变异构体对，进行了N-H...O <--> N...H-O质子转移反应过渡态的计算。表征了这些物种的几何和能量参数。还分析了源自巴德理论的拓扑参数；这些是氢键临界点以及环临界点的特征。除了N-H...O和O-H...N分子内氢键外，还存在其他分子内相互作用，主要是离子相互作用，如Be(+δ)...(-δ)O、Li(+δ)...(-δ)O和Li(+δ)...(-δ)F。对于所研究的一些物种也存在F...O相互作用。由于存在相应的键径和临界点，它们可被归类为能量稳定的相互作用。检测并描述了几何、拓扑和能量参数之间的众多相关性和依赖性。
