从一个偏磁的,单核的超硫 (II) 复合物到一个具有四硫二电子键的二磁二聚体
Shenglai Yao1, Carsten Milsmann, Eckhard Bill
1Metalorganics and Inorganic Materials, Institute of Chemistry, Technische Universität Berlin, Strasse des 17, Juni 135, Sekr. C2, D-10623 Berlin, Germany.
Journal of the American Chemical Society
|September 23, 2008
概括
研究人员合成了第一个可分离的 (II) 超硫化物复合物,其中包括难以捉摸的S2-. 一个连接体. 连接体. 这种偏磁复合体二重化,形成具有独特的四硫键的二磁性物种.
科学领域:
- 无机化学 无机化学 有机化学
- 有机金属化学 有机金属化学
- 硫化学 硫的化学
背景情况:
- 超硫化物 (S2^2-) 连接体具有高度反应性,并且很难在稳定的协调复合体中分离出来.
- 之前的研究集中在过渡性或较少特征的超硫化物复合物的形式上.
- 了解硫联体的协调化学对于催化和材料科学至关重要.
研究的目的:
- 合成和表征第一个可分离的"侧面" (II) 超硫化物复合物.
- 研究合成的超硫化物复合物及其二次体的结构和电子特性.
- 为了探索硫转移反应中超硫化物复合物的反应性.
主要方法:
- 通过轻易氧化合成一个的前体 (I) 与元素硫.
- 使用X射线衍射分析进行结构性表征.
- 光谱分析包括1H NMR,EPR和SQUID磁力测量.
- 使用密度函数理论 (DFT) 计算的计算研究.
主要成果:
- 成功合成了第一个可分离的"侧面"(II) 超硫化物复合物 (1).
- 证明了对磁性超硫化物复合物 (1) 的自发二聚变为具有四硫,两电子键的二磁性二聚物 (1(2) 的证明.
- 证据表明,超硫化物复合物具有将硫转移到素配体和前体的能力,形成二硫化物复合物 (3).
结论:
- 该研究报告了在 (II) 复合体中难以捉摸的S2^2-连接体的稳定和分离.
- 分解行为突出显示了聚硫化连体的新型结合模式.
- 合成的超硫化物复合物作为二硫化物复合物和硫转移反应的宝贵前体.
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