Guo Xin, An Xiulin, Li Qingzhong
†The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People's Republic of China.
‡College of Life Science, Yantai University, Yantai 264005, People's Republic of China.
J Phys Chem A. 2015 Apr 9;119(14):3518-27. doi: 10.1021/acs.jpca.5b00783. Epub 2015 Mar 27.
Quantum-chemical calculations have been performed for the chalcogen- and halogen-bonded complexes of F2CSe with a series of nitrogen bases (N2, NCH, NH3, NHCH2, NCLi, and NMe3) and dihalogen molecules (BrCl, ClF, and BrF), respectively. Both types of interactions are mainly driven by the electrostatic and orbital interactions. The chalcogen bond becomes stronger in the order of NCH (sp) < NH3 (sp(3)) < NHCH2 (sp(2)), showing some inconsistence with the electronegativity of the hybridized N atom. The Li and methyl groups have an enhancing effect on the strength of chalcogen bond; however, the former is jointly achieved through the electrostatic and orbital interactions, whereas the orbital interaction has dominant contribution to the latter enhancement. The halogen bond with F2CX (X = O, S, Se) as the electron donor is stronger for the heavier chalcogen atom, exhibiting a reverse dependence on the chalcogen atom with that in hydrogen bonds. The halogen bond is further strengthened by the presence of chalcogen bond in the ternary complexes. In addition, CSD research confirms the abundance of Se···N interaction in crystal materials.
已分别对二氟二硒与一系列氮碱（N₂、NCH、NH₃、NHCH₂、NCLi和NMe₃）以及二卤分子（BrCl、ClF和BrF）形成的硫族元素键和卤键配合物进行了量子化学计算。这两种相互作用主要由静电相互作用和轨道相互作用驱动。硫族元素键按NCH（sp）＜NH₃（sp³）＜NHCH₂（sp²）的顺序变强，这与杂化N原子的电负性存在一些不一致。锂和甲基对硫族元素键的强度有增强作用；然而，前者是通过静电相互作用和轨道相互作用共同实现的，而轨道相互作用对后者的增强起主要作用。以F₂CX（X = O、S、Se）作为电子供体的卤键，对于较重的硫族元素原子更强，这与氢键中对硫族元素原子的依赖关系相反。在三元配合物中，硫族元素键的存在进一步增强了卤键。此外，剑桥晶体结构数据库（CSD）研究证实了晶体材料中硒···氮相互作用的丰富性。
