Xu Zhefeng, Li Yan
Department of Chemical Engineering, Inner Mongolia Vocational College of Chemical Engineering, Hohhot, 010070, People's Republic of China.
J Mol Model. 2019 Jul 12;25(8):219. doi: 10.1007/s00894-019-4089-1.
The influence of hybridization, substitution, and solvation on the triel bond has been investigated in the complexes of RZH···NH (Z = B and Al). The magnitude of the π-hole on the triel atom is related to the nature of the Z atom and the hybridization of R. CHBH has the largest π-hole among RBH, while for RAlH the largest π-hole is found in CH≡CAlH. The interaction energy is partly inconsistent with the magnitude of the π-hole on the triel atom and the orbital interaction from the N lone pair of NH into the empty p orbital of the triel atom. The strongest B···N triel bond is found in CH≡CBH···NH, while the weakest Al···N triel bond is in CHAlH···NH. The strength of the triel bond is increased in solvents, and its enhancement is prominent with the increase of solvent polarity. Solvents also change the nature of the Al···N triel bond from an electrostatic interaction to a partially covalent one. The F substituent in the triel donor strengthens the triel bond, depending on the substitution position and number. Graphical Abstract The π-hole triel bonded complexes between RZH2 (Z =B and Al) and NH3 have been investigated. We focused on the effects of hybridization, solvent, and substitution on the strength and nature of π-hole triel bond.
在RZH···NH（Z = B和Al）配合物中研究了杂化、取代和溶剂化对三族元素键的影响。三族元素原子上π空穴的大小与Z原子的性质和R的杂化有关。在RBH中，CHBH的π空穴最大，而对于RAlH，在CH≡CAlH中发现最大的π空穴。相互作用能与三族元素原子上π空穴的大小以及从NH的N孤对进入三族元素原子空p轨道的轨道相互作用部分不一致。在CH≡CBH···NH中发现最强的B···N三族元素键，而在CHAlH···NH中Al···N三族元素键最弱。在溶剂中三族元素键的强度增加，并且随着溶剂极性的增加其增强显著。溶剂还将Al···N三族元素键的性质从静电相互作用改变为部分共价相互作用。三族元素供体中的F取代基会增强三族元素键，这取决于取代位置和数量。图形摘要 研究了RZH2（Z = B和Al）与NH3之间的π空穴三族元素键合配合物。我们重点关注了杂化、溶剂和取代对π空穴三族元素键的强度和性质的影响。
