[SF3]+的合成和活性与有机基添加剂
Felix O'Donnell1, Praveen Chaudhary1, Yoyo Yao1
1Canadian Centre for Research in Advanced Fluorine Technologies and Department of Chemistry and Biochemistry, University of Lethbridge, 4401 University Dr W, Lethbridge T1K 3M4, Canada.
Inorganic chemistry
|July 28, 2025
概括
硫四化物 (SF4) 与化化的反应产生SF3+添加物. 这些添加物的结构,比如[SF3(py) ]+和[SF3(dmap) ]+,取决于皮里丁配体,影响稳定性和反应性.
科学领域:
- 无机化学 无机化学
- 有机硫化学 有机硫化学
- 协调化学 协调化学
背景情况:
- 由于其独特的结合和反应性,SF3+离子的化学性感兴趣.
- 了解SF3+与含配体的协调行为对于开发新的合成方法至关重要.
研究的目的:
- 为了研究合成和结构性特征的SF3+添加物与氨酸和4-二甲基亚胺氨酸 (DMAP).
- 探索连接物结构对SF3+复合物的稳定性和同位素偏好的影响.
- 检查SF3+及其添加物与各种核友的反应性.
主要方法:
- SF4与化二烯衍生物的反应, [(CH3) 3Si (((py) ]][OTf]和 [(CH3) 3Si ((dmap) ]][OTf].
- 由此产生的盐的分离和表征,包括[SF3(py) ]][OTf]和[SF3(dmap) ]][OTf].
- 核磁共振光谱用于SF3+复合物的结构阐明.
- 量子化学计算以确定异构体的相对能量.
- [SF3][SbF6]与DMAP的反应以及试图与OPPh3.3形成 adducts的尝试.
主要成果:
- 获得了接近[SF3(py]][OTf]的数量产量.
- [SF3(dmap) ]][OTf]形成的数量很少,并且很容易转化为[SF2(dmap) ][OTf]2和SF4.
- 核磁共振 (NMR) 数据显示[SF3(dmap) ]+的波结构与DMAP的赤道结构,与[SF3(py) ]+中的轴性二烯相反.
- 气相计算显示,轴向[SF3(py) ]+更稳定,而[SF3(dmap) ]+异构体几乎具有同能性.
- 从[SF3][SbF6]和DMAP反应中分离出[SF2(dmap) ]2][SbF6]2.
- 在[SF2[dmap]2]2+中合的合物导致[SF[dmap]4]3+的降水.
- 与OPPh3的反应导致脱氧化,形成[FPPh3]+盐.
结论:
- 联体的协调模式 (pyridine与DMAP) 显著影响SF3+添加物的结构和稳定性.
- DMAP的电子性质有利于赤道协调,并导致容易变异和进一步的连接体杂乱.
- [SF3]+可以充当易斯酸,促进氧化的脱氧化.
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