Gauging the Steric Effects of Silyl Groups with a Molecular Balance.

We present an experimental and computational study of a cyclooctatetraene (COT)-based molecular balance disubstituted with commonly used silyl groups. Such groups often serve as protecting groups and are typically considered innocent bystanders. Our motivation here is to determine the actual steric effects of such groups by employing a molecular balance. While in the unfolded 1,4-valence isomer the silyl groups are far apart ( d _σ-σ ≥ 5.15 Å), the folded 1,6-isomer is affected greatly by noncovalent interactions due to close σ-σ contacts ( d _σ-σ ≤ 2.58 Å). In order to investigate the thermodynamic equilibrium between the 1,6- and 1,4-valence isomers, we employed temperature-dependent nuclear magnetic resonance measurements. Additionally, we assessed the nature of attractive and repulsive interactions in 1,6-disilyl-COT derivatives via a combination of local energy decomposition analysis (LED) and symmetry-adapted perturbation theory (SAPT) at the DLPNO-CCSD(T)/def2-TZVP and sSAPT0/aug- cc -pVDZ levels of theory. We identified London dispersion interactions as the main contributor to the molecular stability of the folded states, whereas Pauli exchange repulsion and a resulting internal strain favor the unfolded diastereomer.