Xu Bing, Shi Peipei, Huang Tengfei, Wang Xuefeng, Andrews Lester
School of Chemical Science and Engineering, Shanghai Key Lab of Chemical Assessment and Sustainability, Tongji University , Shanghai, 200092, China.
Department of Chemistry, University of Virginia , Charlottesville, Virginia 22904 United States.
J Phys Chem A. 2017 May 25;121(20):3898-3908. doi: 10.1021/acs.jpca.6b12217. Epub 2017 May 12.
Infrared spectra of matrix isolated dibridged Si(μ-H)MH and tribridged Si(μ-H)MH molecules (M = Zr and Hf) were observed following the laser-ablated metal atom reactions with SiH 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, MH and hydrogen bridge Si-H-M stretching modes, were confirmed by the appropriate SiD 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···M agostic interaction in terms of electron localization function (ELF) analysis and noncovalent interaction index (NCI) calculations. Furthermore, the different products of Ti, Zr, and Hf reactions with SiH are discussed in detail.
在过量氩气和氖气冷凝过程中，通过激光烧蚀金属原子与硅烷的反应，观测到了基质隔离的双桥联硅（μ-H）MH和三桥联硅（μ-H）MH分子（M = Zr和Hf）的红外光谱，但用钛反应时仅观测到了后一种物质。主要振动模式的归属，包括末端MH、MH和氢桥Si-H-M伸缩模式，通过适当的SiD同位素位移和密度泛函振动频率计算（B3LYP和BPW91）得到了证实。硅-氢-金属氢桥键经计算为弱共价相互作用，并根据电子定位函数（ELF）分析和非共价相互作用指数（NCI）计算，与C-H···M弯曲相互作用进行了比较。此外，还详细讨论了钛、锆和铪与硅烷反应的不同产物。
