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

The quantum mechanical force fields (QMFF's) of 3,3-dimethyl-1-(tert-butyl)cyclopropene (I), 3,3-dimethyl-1-(trimethylsilyl)cyclopropene (II), 3,3-dimethyl-1-(trimethylgermyl)cyclopropene (III), and 3,3-dimethyl-1-(trimethylstannyl)cyclopropene (IV) were calculated at the HF/3-21G*//HF/3-21G* level. The set of scale factors for the correction of HF/3-21G*//HF/3-21G* QMFF of II was determined using its well-characterised vibrational spectrum. Transferral of the set of scale factors obtained for II to the QMFF's of I, III and IV and calculation of the fundamental frequencies resulted in good agreement between the calculated and previously assigned experimental frequencies of III. This again demonstrates the feasibility of transferral of a set of scale factors obtained for the correction of the QMFF of a molecule to others containing heteroatoms from the same column of the Mendeleyev Periodic Table. Thus the calculations performed permitted the accurate assignment of the fundamental vibrational frequencies in the experimental IR spectrum of IV. The vibrational frequencies of 3,3-dimethyl-1-(tert-butyl)cyclopropene (I) were also calculated from the HF/6-31G*//HF/6-31G* QMFF, scaled by the set of scale factors used previously for the HF/6-31G*//HF/6-31G* QMFF's of II and III. Regularities in the trends of some vibrational frequencies with increasing atomic number of the heteroatom are observed.