Comparison of tetrel bonds and halogen bonds in complexes of DMSO with ZF(3)X (Z = C and Si; X = halogen)
Comparison of tetrel bonds and halogen bonds in complexes of DMSO with ZF(3)X (Z = C and Si; X = halogen)
复制标题
DMSO 与 ZF(3)X 络合物中四键和卤素键的比较（Z = C 和 Si；X = 卤素）
DOI：
10.1039/c6ra18316f
复制
发表时间：
2016
期刊：
影响因子：
3.9
通讯作者：
Li Hai-Bei
中科院分区：
文献类型：
--
作者：
Wei Quanchao;Li Qingzhong;Cheng Jianbo;Li Wenzuo;Li Hai-Bei
在MP2/aug-cc-pVTZ水平上对ZF_3X（Z = C和Si; X =卤素）与二甲基亚砜（DMSO）形成的配合物进行了理论研究.在DMSO-ZF 3X复合物的电势表面上发现了三个局部极小值，分别与O Z和O X接触形成四重键和卤键。除CF_4外，卤素键合的配合物对CF_3X比SiF_3X更稳定，而四元键合的配合物DMSO-SiF_3X比类似物DMSO-CF_3X更稳定。DMSO-CF_3X中四元键的强度与卤素原子的性质关系不大，DMSO-SiF_3X中四元键的强度与卤素原子的性质关系异常，DMSO-SiF_3X中四元键的强度比以阴离子为给电子体时的强，表现出部分共价键的性质。在大多数配合物中观察到SO伸缩振动的红移，特别是在DMSO-SiF 3X的四元键合配合物中。Z-X伸缩振动在四元键中表现出红移，但在卤键中表现出不规则的位移。
A theoretical study of the complexes formed by dimethylsulfoxide (DMSO) with ZF3X (Z = C and Si; X = halogen) has been performed at the MP2/aug-cc-pVTZ level. Three local minima were found on the potential surface of complex DMSO–ZF3X, forming tetrel bonds and halogen bonds with O⋯Z and O⋯X contacts, respectively. The halogen-bonded complexes are more stable for CF3X than for SiF3X with an exception of CF4, on the contrary, the tetrel-bonded complexes DMSO–SiF3X are more stable than the analogues DMSO–CF3X. The strength of the tetrel bonds in DMSO–CF3X has a small dependence on the nature of the halogen atom, and DMSO–SiF3X has an abnormal dependence on it. Surprisingly, the tetrel bond in DMSO–SiF3X is stronger than that with an anion as the electron donor, exhibiting a partially covalent bond nature. A red shift was observed for the SO stretch vibration in most complexes, particularly in the tetrel-bonded complexes of DMSO–SiF3X. The Z–X stretch vibration exhibits a red shift in the tetrel bond but an irregular shift in the halogen bond.