理论和实验表明Sb(V) 促进的甲C-H激活和功能化超过硫酸中的超酸质解
Shu-Sen Chen1, Anjaneyulu Koppaka2, Roy A Periana2
1Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, United States.
强酸中的反通过内部球机制激活甲C-H键,产生甲基二硫酸盐. 这种途径超过了传统的超酸质解,挑战了强酸中的反应性假设.
科学领域:
- 无机化学
- 催化剂
- 计算化学
背景情况:
- 在强的布伦斯特德酸中,抗 (V) 传统上通过超酸质解与发生反应.
- 这种假设的机制导致碳酸盐,H2和寡合.
研究的目的:
- 研究甲与硫酸和中的反的反应性.
- 探索超酸质解之外的其他反应机制.
主要方法:
- 密度函数理论 (DFT) 计算用于机械洞察.
- 在180°C的硫酸/中对甲进行实验反应.
- 反应产物的分析,包括甲基二硫酸盐和过氧化产物.
主要成果:
- DFT揭示了一种可访问的C-H激活途径,用于与Antimony ((V) 竞争的甲.
- 实验反应产生了高度的甲基二硫酸盐与最小的过氧化.
- 计算支持C-H激活/Sb-Me键的功能化作为主要机制,解释了H-D交换等实验观测.
结论:
- 强Brønsted酸中的可以促进甲的内部球C-H激活,类似于过渡金属.
- 这种机制挑战了长期以来的超酸质解作为唯一的反应途径的假设.
- 这些发现为超酸性介质中的功能化开辟了新的途径.
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