The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai, 264005, People's Republic of China.
J Mol Model. 2013 Oct;19(10):4529-35. doi: 10.1007/s00894-013-1969-7. Epub 2013 Aug 16.
Quantum chemical calculations have been per-formed for the complexes of formamidine (FA) and hypohalous acid (HOX, X = F, Cl, Br, I) to study their structures, properties, and competition of hydrogen bonds with halogen bonds. Two types of complexes are formed mainly through a hydrogen bond and a halogen bond, respectively, and the cyclic structure is more stable. For the F, Cl, and Br complexes, the hydrogen-bonded one is more stable than the halogen-bonded one, while the halogen-bonded structure is favorable for the I complexes. The associated H-O and X-O bonds are elongated and exhibit a red shift, whereas the distant ones are contracted and display a blue shift. The strength of hydrogen and halogen bonds is affected by F and Li substitutents and it was found that the latter tends to smooth differences in the strength of both types of interactions. The structures, properties, and interaction nature in these complexes have been understood with natural bond orbital (NBO) and atoms in molecules (AIM) theories.
已对甲脒（FA）和次卤酸（HOX，X = F、Cl、Br、I）的配合物进行了量子化学计算，以研究它们的结构、性质以及氢键与卤键的竞争。主要通过氢键和卤键形成两种类型的配合物，并且环状结构更稳定。对于 F、Cl 和 Br 配合物，氢键配合物比卤键配合物更稳定，而卤键结构有利于 I 配合物。相关的 H-O 和 X-O 键被拉长并显示红移，而较远的键被收缩并显示蓝移。氢键和卤键的强度受 F 和 Li 取代基的影响，发现后者趋于平滑两种相互作用强度的差异。已使用自然键轨道（NBO）和分子中的原子（AIM）理论理解了这些配合物中的结构、性质和相互作用性质。
