Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, trimethylgermyl, trimethylstannyl, and trimethylplumbyl derivatives of 3,3-dimethylcyclopropene

The changes in the vibrational frequencies of 1-tert-butyl and 1,2-di-tert-butyl derivatives of 3,3-dimethylcyclopropene brought about by substitution of the central carbon atom (X) of the tert-butyl moieties by Si, Ge, Sn, or Pb atoms are examined. The most important decrease in the vibrational frequencies implicating the X(CH3)3 moieties is noted for substitution of X = C by Si. The substitutions of Si by Ge or Ge by Sn or Sn by Pb are not accompanied by the pronounced frequency shifts observed for the C → Si transition. An explanation is given for trends in these vibrational frequencies for the transitions X = C → Si → Ge → Sn → Pb. It is concluded that there are lower limiting values of the vibrational frequencies of a molecular moiety which are approached when the mass of its isovalent atom is increased. This leads to the formation of cluster regions in the vibrational spectra for the frequencies of the SnC3 and PbC3 moieties.