Abstract
Ab initio calculations have been performed for the complexes of DMSO and phenyltrifluorosilane (PTS) and its derivatives with a substituent of NH3, OCH3, CH3, OH, F, CHO, CN, NO2, and SO3H. It is necessary to use sufficiently flexible basis sets, such as aug’-cc-pVTZ, to get reliable results for the Si···O tetrel bonds. The tetrel bond in these complexes has been characterized in views of geometries, interaction energies, orbital interactions and topological parameters. The electron-donating group in PTS weakens this interaction and the electron-withdrawing group prominently strengthens it to the point where it exceeds that of the majority of hydrogen bonds. The largest interaction energy occurs in the p-HO3S-PhSiF3···DMSO complex, amounting to −122 kJ/mol. The strong Si···O tetrel bond depends to a large extent on the charge transfer from the O lone pair into the empty p orbital of Si, although it has a dominant electrostatic character. For the PTS derivatives of NH2, OH, CHO and NO2, the hydrogen bonded complex is favorable to the tetrel bonded complex for the NH2 and OH derivatives, while the σ-hole interaction prefers the π-hole interaction for the CHO and NO2 derivatives.
Highlights
The tetrel bond has attracted more attention due to its potential applications in crystal materials [1,2,3], chemical reactions [4,5,6], and biological systems [7]
The attractive interaction between a Group 14 atom and a Lewis base has been understood with molecular electrostatic potentials (MEPs), and it was found that there is a region with positive MEPs (σ-hole) at the outer side of the tetrel atom [16]
We study the tetrel bonded complex between phenyltrifluorosilane (PTS) and dimethyl sulfoxide (DMSO)
Summary
The tetrel bond has attracted more attention due to its potential applications in crystal materials [1,2,3], chemical reactions [4,5,6], and biological systems [7]. The Lewis bases in tetrel bonds are usually nitrogen- and oxygen-containing molecules, though other types of Lewis bases are found [8,9,10,11] This attractive interaction has been reported in some simple complexes of SiF4 ···NH3 [12,13,14]. When NH3 approaches XCN (X = F, Cl, Br, I) along its molecular axis or a perpendicular π-hole on the carbon atom, a σ-hole halogen bond and a π-hole tetrel bond are formed, respectively [33] The latter geometry is favored for X = F and the σ-hole structure is preferred for the heavier halogens. The competition between the tetrel bond and other interactions is studied
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