矩阵隔离IR光谱检测S-H···S-S H-键在H2S-二甲基二硫化物复合体中的S-H···S-S H-键
Ankita Kothari1, Binod Kumar Oram1,2,3, Biman Bandyopadhyay1
1Department of Chemistry, Malaviya National Institute of Technology Jaipur, J L N Marg, Jaipur 302017, India.
硫化 (H2S) 与二甲基二硫化 (DEDS) 形成多个S-H··S-S键. 与H2S中的硫相比,DEDS中的S-S键是一个优越的键受体.
科学领域:
- 物理化学 物理化学
- 频谱学是一种光谱学.
- 计算化学计算化学
背景情况:
- 键在分子相互作用中起着至关重要的作用.
- 与以氧为中心的相比,以硫为中心的键的探索较少.
- 乙二硫化物 (DEDS) 含有一种反应性S-S键,能够参与非共价相互作用.
研究的目的:
- 研究H2S和DEDS之间的S-H··S-S键的形成和特征.
- 为了比较DEDS中的S-S连接与其他含硫分子的结能力.
- 探索矩阵环境 (与) 对复合体稳定性和形成的影响.
主要方法:
- 福利埃变换红外光谱法 (FTIR) 用于研究固体和矩阵中的复合物.
- 计算方法被用来计算复杂的相互转换的结合能和激活障碍.
- 对光谱变化和频段强度的分析提供了有关键强度和数量的见解.
主要成果:
- 1:1的H2S与DEDS的复合物被成功识别出来,形成一个或两个S-H·S-S键.
- 在DEDS的两个最低能量的旋转器中观察到五个不同的H键复合体.
- 结合能从2.43到3.05 kcal mol-1不等,激活障碍从0.08到2.65 kcal mol-1.1不等.
- DEDS中的S-S连接被证明是一个比H2S中的硫原子更有效的键受体.
- 由于矩阵效应,在N2矩阵中比Ar矩阵更容易观察到复合物.
结论:
- DEDS中的S-S键是S-H键的高效接受器.
- 散射相互作用对这些以硫为中心的结合复合物的稳定有显著的贡献.
- 这项研究提供了关于硫中心键性质的宝贵数据,扩大了我们对非共价相互作用的理解.
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