Journal of Physical Chemistry A, Vol.122, No.1, 81-88, 2018
Matrix-Infrared Spectra and Structures of HM-SiH3 (M = Ge, Sn, Pb, Sb, Bi, Te Atoms)
The reactions of Ge, Sn, Pb, Sb, Bi, and Te atoms with silane molecules were studied using matrix-isolation Fourier transform infrared spectroscopy and density functional theoretical (DFT) calculations. All metals generate the inserted complexes HM-SiH3, which were stabilized in an argon matrix, while H2M=SiH(2 )and H3M SiH were not observed. DFT and CCSD(T) calculations show the insertion complex HM-SiH(3 )is the most stable isomer with a near right angle H-M-Si moiety. However, silydene complexes H2M=SiH2 (M = C, Si) were calculated and identified as the most stable complexes with the lighter elements. The bonding difference is mainly due to relativistic effects, which is that for heavier metal atoms valence s and p orbitals have a lower tendency to form hybrid orbitals.