Department of Chemistry, Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji University, Shanghai, 200092, China.
Phys Chem Chem Phys. 2014 Feb 14;16(6):2607-20. doi: 10.1039/c3cp53811g.
Coinage metal atom (Cu, Ag, Au) reactions with SO2 were investigated by matrix isolation infrared absorption spectroscopy and density functional theory electronic structure calculations. Both mononuclear complexes M(η(1)-SO2) (M = Ag, Au) and M(η(2)-O2S) (M = Ag, Cu) were observed during condensation in solid argon or neon. Interestingly, the silver containing mononuclear complexes are interconvertible; that is, visible light induces the isomerization of Ag(η(1)-SO2) to Ag(η(2)-O2S) and vice versa on annealing. However, there is no evidence of similar interconvertibility for the Cu(η(2)-O2S) and Au(η(1)-SO2) molecules. These different behaviors are discussed within the bonding considerations for all of the obtained products.
采用基质隔离红外吸收光谱和密度泛函理论电子结构计算研究了金属原子(Cu、Ag、Au)与 SO2 的反应。在固体氩或氖中冷凝时,观察到单核配合物 M(η(1)-SO2)(M = Ag、Au)和 M(η(2)-O2S)(M = Ag、Cu)。有趣的是,含银的单核配合物是可互变的;也就是说,可见光诱导 Ag(η(1)-SO2)异构化为 Ag(η(2)-O2S),反之亦然,退火时也如此。然而,Cu(η(2)-O2S)和 Au(η(1)-SO2)分子没有类似的互变证据。这些不同的行为是在对所有获得的产物的成键考虑的基础上讨论的。