Hydrogen-bridge Si(μ-H)3CeH and inserted H3SiCeH molecules: Matrix infrared spectra and DFT calculations for reaction products of silane with Ce atoms

作者：Xu, Bing; Shi, Peipei; Huang, Tengfei; Wang, Xuefeng^*

来源：Journal of Molecular Structure, 2017, 1146: 692-702.

DOI：10.1016/j.molstruc.2017.05.113

• Hydrogen bridge bond
• Matrix isolation
• Transition metal
• DFT calculation

Reactions of laser-ablated cerium atoms with silane were investigated by matrix isolation infrared spectroscopy and theoretical calculations. The reaction products, Si(mu-H)(3)CeH, H3SiCeH, H2Si(mu-H)CeH and HSi(mu-H)(2)CeH were identified on the basis of the SiD4 isotopic substitutions and DFT frequency calculations. In the solid argon or krypton matrix, the inserted H3SiCeH molecule was observed as initial product on deposition, which rearranged to hydrogen bridge species Si(mu-H)(3)CeH on follow-up annealing through H2Si(mu-H)CeH and HS(mu-H)(2)CeH species. The Si-H-Ce hydrogen bridge was investigated by NBO and ELF analysis. Calculation suggested that in Si(mu-H)(3)CeH molecule Ce atom donated one electron to Si atom, resulting in electron-rich SiH3 subunit, which was confirmed by ESP and AIM analysis. The increased basicity of Si-H bond facilitates the formation of hydrogen bridge bond between Si and Ce. For comparison only insertion H3CCeH structure was obtained from the reaction of Ce atoms with CH.

• 出版日期2017-10-15
• 单位同济大学