C∙∙∙O 和 Si∙∙∙O 四中心键：取代基效应和 SiF 基团的转移。
C∙∙∙O and Si∙∙∙O Tetrel Bonds: Substituent Effects and Transfer of the SiF Group.
机构信息
The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China.
Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322, USA.
出版信息
Int J Mol Sci. 2023 Jul 25;24(15):11884. doi: 10.3390/ijms241511884.
The tetrel bond (TB) between 1,2-benzisothiazol-3-one-2-TF-1,1-dioxide (T = C, Si) and the O atom of pyridine-1-oxide (PO) and its derivatives (PO-X, X = H, NO, CN, F, CH, OH, OCH, NH, and Li) is examined by quantum chemical means. The Si∙∙∙O TB is quite strong, with interaction energies approaching a maximum of nearly 70 kcal/mol, while the C∙∙∙O TB is an order of magnitude weaker, with interaction energies between 2.0 and 2.6 kcal/mol. An electron-withdrawing substituent on the Lewis base weakens this TB, while an electron-donating group has the opposite effect. The SiF group transfers roughly halfway between the N of the acid and the O of the base without the aid of cooperative effects from a third entity.
通过量子化学方法研究了 1,2-苯并异噻唑-3-酮-2-TF-1,1-二氧化物（T = C, Si）与吡啶-1-氧化物（PO）及其衍生物（PO-X，X = H, NO, CN, F, CH, OH, OCH, NH, 和 Li）中 O 原子之间的四中心键（TB）。Si∙∙∙O TB 非常强，相互作用能接近最大值近 70 kcal/mol，而 C∙∙∙O TB 弱一个数量级，相互作用能在 2.0 到 2.6 kcal/mol 之间。路易斯碱上的吸电子取代基会削弱这种 TB，而给电子基团则会产生相反的效果。SiF 基团在没有第三个实体协同作用的情况下，在酸的 N 和碱的 O 之间转移了大约一半的位置。
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