Aryl-Aryl Interactions in (Aryl-Perhalogenated) 1,2-Diaryldisilanes.

Three 1,2-diaryltetramethyldisilanes X5 C6 -(SiMe2 )2 -C6 X5 with two C6 H5 , C6 F5 , or C6 Cl5 groups were studied concerning the importance of London dispersion driven interactions between their aryl groups. They were prepared from 1,2-dichlorotetramethyldisilane by salt elimination. Their structures were determined in the solid state by X-ray diffraction and for free molecules by gas electron-diffraction. The solid-state structures of the fluorinated and chlorinated derivatives are dominated by aryl-aryl interactions. Unexpectedly, Cl5 C6 -(SiMe2 )2 -C6 Cl5 exists exclusively as an eclipsed syn-conformer in the gas phase with strongly distorted Si-C6 Cl5 units due to strong intramolecular interactions. In contrast, F5 C6 -(SiMe2 )2 -C6 F5 reveals weaker interactions. The contributions to the total interaction energy were analyzed by SAPT calculations.