Department of Chemistry and Biochemistry, Nanoscale and Quantum Phenomena Institute, Ohio University, Athens, Ohio 45701, USA.
Inorg Chem. 2010 May 17;49(10):4466-70. doi: 10.1021/ic902047f.
We report the structure, electrochemistry, and isomerization kinetics for Ru(bpy)(biq)(OSO), where bpy is 2,2'-bipyridine, biq is 2,2'-biquinoline, and OSO is 2-methylsulfinylbenzoate. UV-visible and infrared data are suggestive of intramolecular S-->O and O-->S isomerization of the sulfoxide. Cyclic voltammetry reveals evidence for isomerization triggered by oxidation and reduction. Of particular note is the variation of the S-->O isomerization rate constant in different solvents. The rates were found to be 3.2 (+/-0.4) s(-1) in propylene carbonate, 0.80 (+/-0.03) s(-1) in acetonitrile, and 0.26 (+/-0.01) s(-1) in dichloromethane.
我们报告了Ru(bpy)(biq)(OSO)的结构、电化学和异构化动力学，其中 bpy 是 2,2'-联吡啶，biq 是 2,2'-联喹啉，OSO 是 2-甲基亚磺酰基苯甲酸酯。紫外可见和红外数据表明亚砜的分子内 S-->O 和 O-->S 异构化。循环伏安法显示出氧化和还原引发异构化的证据。特别值得注意的是不同溶剂中 S-->O 异构化速率常数的变化。在碳酸丙烯酯中，速率常数为 3.2(+/-0.4)s(-1)，在乙腈中为 0.80(+/-0.03)s(-1)，在二氯甲烷中为 0.26(+/-0.01)s(-1)。
