在11个顶点的Rhodathiaborane上进行基化,并完全参与集群
Alvaro Alvarez1, Ramón Macías, Jonathan Bould
1Departamento de Química Inorgánica, Instituto Universitario de Catálisis Homogénea, Universidad de Zaragoza-Consejo Superior de Investigaciones Científicas, 50009-Zaragoza, Spain.
Journal of the American Chemical Society
|August 6, 2008
概括
这项研究详细介绍了新型-硫-集群的合成和反应性,通过拟议的nido-to-closo转换机制证明了其对基化的催化潜力.
科学领域:
- 有机金属化学 有机金属化学
- 化学 化学
- 催化剂是一种催化剂.
背景情况:
- 金属乙烯基具有独特的结构和反应性.
- 了解nido转化为closo结构对于催化应用至关重要.
- 由于潜在的催化活性,罗达提亚波兰具有兴趣.
研究的目的:
- 为了合成和表征一种新型金属甲, [8,8-(PPh 3) 2-nido-8,7-RhSB 9H 10] (1).
- 为了研究化合物1的反应性,特别是它的转化和催化潜力.
- 阐明由合成集群催化的基化机制.
主要方法:
- 易于合成的金属甲乙烯 [8,8-(PPh 3) 2-nido-8,7-RhSB 9H 10] (1).
- 与, (乙烯) 和一氧化碳的反应.
- 光谱分析 (NMR) 和密度函数理论 (DFT) 的计算.
主要成果:
- 从1.开始合成的nido-hydridorhodathiaborane [8,8,8-(PPh 3) 2H-9-(NC 5H 5) - nido-8,7-RhSB 9H 9] (2) 的合成.
- 克洛索-罗达提亚波兰的形成 [1,1-(PPh 3) ((L) -3- ((NC 5H 5) - 克洛索-RhSB 9H 8] (3, L=C 2H 4; 4, L=CO) 和 [1,1-(PPh 3) 2-3- ((NC 5H 5) - 克洛索-1,2-RhSB 9H 8] (5).
- 由集群催化的基化和异构化的演示,并提出了一种涉及双转移的nido to closo转换机制.
结论:
- - 硫 - 集群系统表现出动态反应性,包括nido-to-closo转换.
- 集群通过拟议的机制作为化的催化剂.
- 对H2激活机制 (单位与集群双功能) 进行进一步的研究是有必要的.
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