Central-atom size effects on the methyl torsions of group XIV tetratolyls

Article abstract of DOI:10.1002/chem.201202105

The Group XIV tetratolyl series X(C₆H₄-CH ₃)₄ (X=C, Si, Ge, Sn, Pb) were studied by using inelastic neutron scattering to measure the low-energy phonon spectra to directly access the methyl-group torsional modes. The effect of increased molecular radius as a function of the size of the central atom was shown to have direct influence on the methyl dynamics, reinforced with the findings of molecular dynamics and contact surface calculations, based upon the solid-state structures. The torsional modes in the lightest analogue were found to be predominantly intramolecular: the Si and Ge analogues have a high degree of intermolecular methyl-methyl group interactions, whilst the heaviest analogues (Sn and Pb) showed pronounced intermolecular methyl interactions with the whole phonon bath of the lattice modes. Size matters! The size of the central atom in the Group XIV tetratolyls was shown to determine the solid-state structures courtesy of the effect that it has on the overall size of the molecules (see figure). Because the outer-most methyl groups enter into close intermolecular interactions (for the Si and Ge analogues), the structure is driven to lower symmetry; as a consequence, the smallest (C) and largest (Sn and Pb) analogues are isostructural. Copyright