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Matrix-Infrared Spectra and Structures of HM–SiH3 (M = Ge, Sn, Pb, Sb, Bi, Te Atoms)

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posted on 2017-12-15, 00:00 authored by Bing 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 H2MSiH2 and H3MSiH 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 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.

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