两类含氧分子形成tetrel bond复合物的理论研究

发布时间：2018-04-28 09:43

本文选题：卤键 + Tetrel　；参考：《烟台大学》2017年硕士论文

【摘要】：Tetrel bond作为一种新型的分子间相互作用,在构建晶体材料、调控化学反应和分子识别中有着重要的应用。本论文利用理论计算方法对tetrel bond的形成、性质和作用规律进行了研究。主要内容如下:二甲亚砜(DMSO)与TF_3X(T=C,Si;X=卤素原子)不仅可以形成tetrel bond,也可以形成卤键。除DMSO···CF_4体系外,DMSO更易于与CF_3X形成卤键,而DMSO更易于与SiF_3X形成tetrel bond。卤原子对DMSO···CF_3X体系中的tetrel bond影响较小,但DMSO···SiF_3X体系中的tetrel bond受卤原子的影响非常大。DMSO···SiF_3X体系中的tetrel bond具有部分共价键的性质,其比阴离子形成的tetrel bond还强。研究了DMSO与苯基三氟硅烷体系中取代基对tetrel bond的影响。当取代基是推电子基NH_3,OCH_3,CH_3和OH时,tetrel bond作用减弱;当取代基是吸电子基F,CHO,CN,NO_2和SO_3H时,tetrel bond作用增强。在p-HO_3S-PhSiF_3···DMSO复合物中作用最强,作用能为-122 kJ/mol。Tetrel bond主要由静电作用主导,不过由O的孤对电子轨道向Si的空p轨道的电荷转移也非常重要。当取代基为NH_2和OH时,其更易于形成氢键;当取代基为CHO和NO_2时,tetrel bond比π-hole作用更强。在PhTH_3···H_3ZO和PhSiF_3···H_3ZO(T=Si,Ge和Sn;Z=N,P和As)复合物中,除了主要的T···O tetrel bond外,还存在其它弱相互作用。这些复合物的结合能从11到220 kJ/mol,T···O距离从1.89到3.09?。对于给定的PhTH_3/PhSiF_3,复合物的稳定性按Z=PAsN顺序增加;对于给定的H_3ZO,结合能还与PhTH_3/PhSiF_3有关。由O的孤对电子轨道到C-T和T-H反键轨道的电荷转移使得这些复合物稳定。PhTH_3/PhSiF_3···H_3ZO中的T···O作用具有很大程度的共价性质,在PhSiF_3···H_3NO中C-Si键和Si-O键的键长几乎相等。
[Abstract]:As a new type of intermolecular interaction, Tetrel bond plays an important role in the construction of crystal materials, the regulation of chemical reactions and molecular recognition. In this paper, the formation, properties and action law of tetrel bond are studied by theoretical calculation method. The main contents are as follows: dimethyl sulfoxide (DMSOs) and TF3XT (CX SiX = halogen atoms) can not only form tetrel bond, but also form halogen bond. In addition to the DMSO CF_4 system, it is easier for DMSO to form a halogen bond with CF_3X, and for DMSO to form tetrel bond with SiF_3X. The effect of halide atoms on tetrel bond in DMSO CF_3X system is small, but tetrel bond in DMSO SiF_3X system is greatly influenced by halide atoms. Tetrel bond in DMSO SiF_3X system has the property of partial covalent bond, which is stronger than tetrel bond formed by anion. The effect of substituents on tetrel bond in the system of DMSO and phenyl trifluorosilane was studied. The effect of tetrel bond is weakened when the substituent is a push-electron group NH _ 3O _ Ch _ 3C _ T _ 3 and OH, while the effect of tetrel bond is enhanced when the substituent is an electron absorbing group. The interaction energy of -122 kJ/mol.Tetrel bond is dominated by electrostatic interaction, but the charge transfer from O's lone pair electron orbital to Si's empty p orbital is also very important. When the substituents are NH_2 and OH, it is easier to form hydrogen bonds, and when the substituents are CHO and NO_2, the effect of tetrel bond is stronger than that of 蟺 -hole. In addition to the main T O tetrel bond, there are other weak interactions in the complexes of PhTH_3 H_3ZO and PhSiF_3 H3ZOTZOGe. The binding energies of these complexes range from 11 to 220 KJ / mol / O from 1.89 to 3.09. For a given PhTH3 / PhSiF3, the stability of the complex increases in Z=PAsN order, and for a given Hs 3ZO, the binding energy is also related to PhTH_3/PhSiF_3. The charge transfer from the solitary pair electron orbital of O to the C-T and T-H antibonding orbitals makes these complexes stable. The T-O interaction in PhTH3 / PhSiFSP _ 3 H_3ZO has a great degree of covalent property. In PhSiF_3 H_3NO, the bond lengths of C-Si bond and Si-O bond are almost equal.
【学位授予单位】：烟台大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3

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