与同结构的二化合物结合 S = 1⁄2 和 S = 0 复合体
Daniel L M Suess1, Charlene Tsay, Jonas C Peters
1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Journal of the American Chemical Society
|August 16, 2012
概括
使用新型辅助联结物合成了具有H(2) 和N(2) 联结物的新复合物. 这些复合体表现出联结体可变性,并确定了它们的结合能量.
科学领域:
- 无机化学 无机化学
- 有机金属化学 有机金属化学
- 协调化学 协调化学
背景情况:
- 复合物在催化和材料科学中至关重要.
- 了解带结合和可变性是设计功能性金属复合物的关键.
- 非经典的H(2) 和N(2) 复合体提供独特的反应途径.
研究的目的:
- 合成和表征新型同结构复合物与H(2) 和N(2) 连接体.
- 为了研究这些复合物的联结平衡和能量学.
- 为了比较复合物的特性与tris(phosphino) silyl和tris(phosphino) borane辅助连接体.
主要方法:
- 通过对比和还原反应合成复合物.
- 使用X射线结晶学和各种光谱技术 (UV/Vis,NMR) 进行表征.
- 使用温度依赖的UV/Vis光谱学和范霍夫分析确定连接体结合能.
主要成果:
- 两种同结构的,非经典的Co ((H ((2)) 和Co ((N ((2)) 复合物使用tris ((phosphino) silyl和tris ((phosphino) borane连接物成功制备.
- 发现H(2) 和N(2) 连接物在环境条件下都是不稳定的.
- 量化了H(2) 和N(2) 结合的热力学参数 (ΔH°, ΔS°).
结论:
- 合成的复合物代表了一类非经典的H(2) 和N(2) 协调化合物.
- H(2) 和N(2) 连接体的可变性是关键特征,使可观测的结合平衡成为可能.
- 确定的能量为这些复合物的稳定性和反应性提供了洞察力,这与未来的催化应用有关.
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