Double and Triple Si-H-M Bridge Bonds: Matrix Infrared Spectra and Theoretical Calculations for Reaction Products of Silane with Ti, Zr, and Hf Atoms

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

来源：Journal of Physical Chemistry A, 2017, 121(20): 3898-3908.

DOI：10.1021/acs.jpca.6b12217

• CARBENE HYDRIDE COMPLEX
• C-H
• AGOSTIC INTERACTIONS
• TITANIUM ATOMS
• ARGON MATRIX
• MOLECULES
• HYDROGEN
• INSERTION
• SI2H2
• PSEUDOPOTENTIALS

Infrared spectra of matrix isolated dibridged Si(mu-H)(2)MH2 and tribridged Si(mu-H)(3)MH molecules (M = Zr and Hf) were observed following the laser-ablated metal atom reactions with SiH4 during condensation in excess argon and neon, but only the latter species was observed with titanium. Assignments of the major vibrational modes, which included terminal MH, MH2 and hydrogen bridge Si-H-M stretching modes, were confirmed by the appropriate SiD4 isotopic shifts and density functional vibrational frequency calculations (B3LYP and BPW91). The Si-H-M hydrogen bridge bond is calculated as weak covalent interaction and compared with the C-H center dot center dot center dot M agostic interaction in terms of electron localization ELF) analysis and noncovalent interaction index (NCI) calculations. Furthermore, the different products of Ti, Zr, and Hf reactions with SiH4 are discussed in detail.

• 出版日期2017-5-25
• 单位同济大学