硫基:气相生成,光异构化和氧化
Jian Xu1, Zhuang Wu1, Huabin Wan1
1College of Chemistry, Chemical Engineering and Materials Science , Soochow University , Suzhou 215123 , China.
Journal of the American Chemical Society
|July 11, 2018
概括
这是第一次在气相中产生硫基. 在紫外线照射下,这些基因异构为新型氧甲基,并经历进一步的转化,产生各种基因物种.
科学领域:
- * 物理化学
- * 有机化学
- * 光谱学
背景情况:
- * 硫酸基是硫化物化学中的关键中间体.
- 在气相中,硫基 (PhSO•) 的生成和光化学行为以前未被探索.
研究的目的:
- * 首次在气相中产生硫基 (PhSO•).
- * 研究PhSO•及其衍生物的光化学异构和反应.
- 使用光谱和计算方法来描述新型基质中间体.
主要方法:
- * 在高真空中燃烧PhS{O) R (R=CF3和Cl) 在~1000K以产生PhSO•.
- * 在低温基质 (2.8K) 中辐射紫外线 (365nm和193nm).
- * PhSO•与分子氧气相反应
- 使用红外和紫外光谱识别中间体.
- * 量子化学计算 (B3LYP/def2-TZVPP和UCCSD)
主要成果:
- 在气相中成功产生硫基 (PhSO•).
- 在紫外线照射下,PhSO• 变异为氧基 (PhOS•).
- * PhOS•进一步异构为2-基基,并经过环开放形成硫基基.
- * 与O2的反应产生基 (Ph•) 和OSOO,或基 (PhO•) 和SO2.
- *光谱和计算数据支持所有观察到的中间体的识别.
结论:
- 这项研究报告了第一个硫基的气相生成.
- * 新的光化学途径涉及硫基和氧基的异构和环开放.
- * 这些发现提供了有关硫化物衍生基的反应性和光化学的见解.
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