posted on 2017-12-15, 00:00authored byBing Xu, Li Li, Peipei Shi, Wenjie Yu, Jie Zhao, Xuefeng Wang, Lester Andrews
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 H2MSiH2 and
H3MSiH were not observed. DFT and CCSD(T) calculations
show the insertion complex HM-SiH3 is the most stable isomer
with a near right angle H–M–Si moiety. However, silydene
complexes H2MSiH2 (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.