Comparison for sigma-hole and pi-hole tetrel-bonded complexes involving cyanoacetaldehyde
Comparison for sigma-hole and pi-hole tetrel-bonded complexes involving cyanoacetaldehyde
复制标题
涉及氰基乙醛的西格玛孔和π孔四重键配合物的比较
DOI：
10.1080/00268976.2017.1377851
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发表时间：
2018
影响因子：
1.7
通讯作者：
Li Qingzhong
中科院分区：
文献类型：
--
作者：
Wei Yuanxin;Li Qingzhong
对氰基乙醛（CA）与TH_3F（T = C，Si，Ge，Sn）和F_2TO（T = C，Si）的配合物进行了从头算研究。TH_3F和F_2TO分别形成σ-空穴和π-空穴四元键配合物。通常，对于每个四元供体，获得三个最小络合物（N、O-A和O-B）。大多数复合物通过一级四重键和二级氢键来稳定。TH_3F-N/F_2CO-N的稳定性比TH_3F-O/F_2CO-O的稳定性好，而F_2SiO的稳定性则相反，尽管它们的相互作用能相当。从CA的N/O原子上的孤对电子到T-F σ* 反键轨道的电荷转移导致TH 3F络合物的稳定化。因此，T-F键被延长，其伸缩振动显示红移。所涉及的单个力的分解的属性的复杂的稳定性主要是静电能，在CH 3F配合物和相对较大的极化能在F2 SiO配合物中的相对较大的色散项。
Ab initiocalculations have been performed for the complexes of cyanoacetaldehyde (CA) with TH3F (T = C, Si, Ge and Sn) and F2TO (T = C and Si). The σ-hole and π-hole tetrel-bonded complexes are formed for TH3F and F2TO, respectively. In general, three minima complexes (N, O–A and O–B) are obtained for each tetrel donor. Most complexes are stabilised by a primary tetrel bond and a secondary hydrogen bonding. TH3F–N/F2CO–N has greater stability than TH3F–O/F2CO–O, but a reverse result is found in the complexes of F2SiO although they have comparative interaction energies. Charge transfer from the lone pair on the N/O atom of CA into the T–F σ*antibonding orbital leads to the stabilisation of the TH3F complexes. Accordingly, the T–F bond is extended and its stretch vibration displays a redshift. A breakdown of the individual forces involved attributes the stability of the complex mainly to electrostatic energy, with relatively large dispersion term in the CH3F complexes and relatively large polarisation energy in the F2SiO complexes.