Li Yan, Xu Zhefeng
Department of Chemical Engineering, Inner Mongolia Vocational College of Chemical Engineering, Hohhot, 010070, People's Republic of China.
J Mol Model. 2018 Aug 20;24(9):247. doi: 10.1007/s00894-018-3732-6.
The complexes formed between TX-ZX (T = C, Si, Ge; Z = P, As, Sb; X = F, Cl) and NH were studied at the MP2/aug-cc-pVTZ(PP) level. For each TX-ZX, two types of complex were obtained. For CX-ZX, NH is inclined to approach the σ-hole on the Z atom, forming a pnicogen bond. For TX-ZX (T = Si and Ge), however, the base favors engaging in a tetrel bond with the σ-hole on the T atom although the corresponding pnicogen-bonded complex is also stable. When NH approaches the CX terminal of CX-ZX, weak interactions are observed that may be classified as van der Waals interactions. The relative stability of both types of complexes is not affected by the substituent X. The tetrel bond is very strong and the largest interaction energy is up to -144 kJ mol. Dispersion is dominant in the weak van der Waals complexes, while tetrel- and pnicogen-bonded complexes are dominated by electrostatic interactions, with comparable contributions from polarization.
在MP2/aug-cc-pVTZ(PP)水平上研究了TX-ZX（T = C、Si、Ge；Z = P、As、Sb；X = F、Cl）与NH形成的配合物。对于每种TX-ZX，得到了两种类型的配合物。对于CX-ZX，NH倾向于靠近Z原子上的σ-空穴，形成一个氮族元素键。然而，对于TX-ZX（T = Si和Ge），尽管相应的氮族元素键合配合物也很稳定，但碱更倾向于与T原子上的σ-空穴形成一个碳族元素键。当NH靠近CX-ZX的CX端时，观察到可能归类为范德华相互作用的弱相互作用。两种类型配合物的相对稳定性不受取代基X的影响。碳族元素键很强，最大相互作用能高达-144 kJ/mol。在弱范德华配合物中色散起主导作用，而碳族元素键合和氮族元素键合配合物则以静电相互作用为主，极化的贡献相当。
