Huang Tengfei, Wang Qiang, Yu Wenjie, Wang Xuefeng, Andrews Lester
School of Chemical Science and Engineering , Tongji University , Shanghai 200092 , P. R. China.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry , Chinese Academy of Sciences , Taiyuan 030001 , P. R. China.
J Phys Chem A. 2018 Jun 21;122(24):5391-5400. doi: 10.1021/acs.jpca.8b03731. Epub 2018 Jun 11.
Infrared absorptions of the matrix isolated OMS, OM(η-SO), and OM(η-SO)(η-OS) (M = Ce, Th) molecules were observed following reactions of laser-ablated Ce and Th metal atoms with SO during condensation in excess argon and neon. Band assignments for the main vibrational modes were confirmed by appropriate SO and SO isotopic shifts. B3LYP, BPW91 density functional, and CASSCF/CASPT2 calculations were performed to characterize these new reaction products and to explore the admixture of f orbitals into the bonding giving stronger M≡O triple bonds. It is very interesting that both OM(η-SO) and OM(η-SO)(η-OS) molecules show chiral structure.
在过量氩气和氖气冷凝过程中，将激光烧蚀的铈（Ce）和钍（Th）金属原子与二氧化硫（SO）反应后，观察到基质隔离的OMS、OM(η-SO)和OM(η-SO)(η-OS)（M = Ce、Th）分子的红外吸收。通过适当的SO和SO同位素位移确认了主要振动模式的谱带归属。进行了B3LYP、BPW91密度泛函以及CASSCF/CASPT2计算，以表征这些新的反应产物，并探索f轨道混入键合中从而形成更强的M≡O三键的情况。非常有趣的是，OM(η-SO)和OM(η-SO)(η-OS)分子均呈现出手性结构。
