Yang Qingqing, Zhang Xiaolong, Li Qingzhong
The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People's Republic of China.
ACS Omega. 2021 Oct 22;6(43):29037-29044. doi: 10.1021/acsomega.1c04085. eCollection 2021 Nov 2.
The tetrel bond formed by HC≡CX, HC=CHX, and HCCHX (X=F, Cl, Br, I) as an electron donor and THF (T=C, Si, Ge) was explored by ab initio calculations. The tetrel bond formed by HCCHX is the strongest, as high as -3.45 kcal/mol for the HCCHF···GeHF dimer, followed by HC=CHX, and the weakest bond is from HC≡CX, where the tetrel bond can be as small as -0.8 kcal/mol. The strength of the tetrel bond increases in the order of C < Si < Ge. For the HCCHX and HC≡CX complexes, the tetrel bond strength shows a similar increasing tendency with the decrease of the electronegativity of the halogen atom. Electrostatic interaction plays the largest role in the stronger tetrel bonds, while dispersion interaction makes an important contribution to the HC=CHX complexes.
通过从头算计算研究了由HC≡CX、HC=CHX和HCCHX（X = F、Cl、Br、I）作为电子供体与THF（T = C、Si、Ge）形成的四元键。由HCCHX形成的四元键最强，对于HCCHF···GeHF二聚体高达-3.45千卡/摩尔，其次是HC=CHX，最弱的键来自HC≡CX，其中四元键可小至-0.8千卡/摩尔。四元键的强度按C < Si < Ge的顺序增加。对于HCCHX和HC≡CX配合物，随着卤原子电负性的降低，四元键强度呈现出类似的增加趋势。在较强的四元键中，静电相互作用起最大作用，而色散相互作用对HC=CHX配合物有重要贡献。
