Tetrel Bonds between Phenyltrifluorosilane and Dimethyl Sulfoxide: Influence of Basis Sets, Substitution and Competition

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.

Competitive tetrel bond and hydrogen bond in benzaldehyde-CO2: Characterization by rotational spectroscopy

The rotational spectrum of the 1:1 benzaldehyde-CO2 complex has been investigated by pulsed-jet Fourier transform microwave spectroscopy complemented with quantum chemical calculations. Two isomers, both characterized by one C···O tetrel...

Origins and Properties of the Tetrel Bond

The tetrel bond (TB) recruits an element drawn from the C,Si,Ge,Sn,Pb family as electron acceptor in an interaction with a partner Lewis base. The underlying principles that explain this attractive...

Promotion of TH3 (T=Si and Ge) group transfer within a tetrel bond by a cation-π interaction

The possibility of the transfer of the TH3 group across a tetrel bond is considered by ab initio calculations. The TB is constructed by pairing PhTH3 (Ph=phenyl; T = Si...