Liu Xing, Liu Xiao-Rui
College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, P. R. China.
Chemistry. 2019 Apr 17;25(22):5698-5707. doi: 10.1002/chem.201806154. Epub 2019 Mar 19.
Infrared spectra of the matrix-isolated Sn(η -O S), Sn(η -OSO), Sn(η -O S)(η -OSO), Sn(η -O S) OSn (η -SO), and Sn(μ -O )SnS molecules were observed following laser-ablated Sn atom reactions with SO during condensation in solid argon. The assignments for the major vibrational modes were confirmed by appropriate S O and SO isotopic shifts and density functional vibrational frequency calculations (B3LYP and BPW91). Interestingly, the mononuclear complexes are interconvertible; that is, irradiation induces the isomerization of Sn(η -O S) and Sn(η -O S)(η -OSO) to Sn(η -OSO) and Sn(η -O S) , respectively, and vice versa on annealing. However, there is no evidence of isomerization reaction in between the binuclear molecules OSn (η -SO) and Sn(μ -O )SnS. Bonding in these products is discussed, and the electronic structure changes associated with different bonding types are revealed, which is crucial for the observed photochemical reactions.
在固体氩气冷凝过程中，观察到激光烧蚀的锡原子与二氧化硫反应后，基质隔离的Sn(η -O S)、Sn(η -OSO)、Sn(η -O S)(η -OSO)、Sn(η -O S) OSn (η -SO)和Sn(μ -O )SnS分子的红外光谱。主要振动模式的归属通过适当的S O和SO同位素位移以及密度泛函振动频率计算（B3LYP和BPW91）得以确认。有趣的是，单核配合物是可相互转化的；也就是说，辐照分别诱导Sn(η -O S)和Sn(η -O S)(η -OSO)异构化为Sn(η -OSO)和Sn(η -O S)，反之，退火时则发生相反的异构化。然而，没有证据表明双核分子OSn (η -SO)和Sn(μ -O )SnS之间存在异构化反应。讨论了这些产物中的键合情况，并揭示了与不同键合类型相关的电子结构变化，这对于观察到的光化学反应至关重要。
