合成稳定的多德卡基基衍生物的hypercloso-B12H12H12的合成
Omar K Farha1, Richard L Julius, Mark W Lee
1Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, California 90095-1569, USA.
Journal of the American Chemical Society
|December 22, 2005
概括
用基化物化克洛索酸盐的化产生多德卡基-克洛索-多德卡酸盐. 这些化合物经历可逆氧化,它们的合成使用自闭槽加速.
科学领域:
- 无机化学 无机化学 有机化学
- 化学 化学
- 超分子化学 超分子化学
背景情况:
- dodecaalkoxy-closo-dodecaborate dianion, [closo-B12(OR) [12]2-,是一种多功能集群,在材料科学中具有潜在的应用.
- 了解这些集群的反应性和氧化还原性质对于它们的合成操作和功能化至关重要.
研究的目的:
- 为了研究化[closo-B12(OH) 12) 2-前体的范围和局限性.
- 探索十二甲基基-密封-二甲基酸衍生物及其氧化形式的合成和氧化还原行为.
- 为了优化合成条件,以便有效地制备这些集群.
主要方法:
- 使用各种基和基化物和托西拉酸盐在N,N-二异乙烯胺的存在下化[closo-B12(OH) 12-2 .
- 使用FeCl3.6H2O或K3Fe (CN) 6.6的化学氧化[closo-B12(OR) [12]2-和[hypercloso-B12(OR) [12]-使用FeCl3.6H2O或K3Fe(CN) 6.
- 使用玻利化的还原过程.
- 合成优化使用高温和压力在一个自闭槽.
- 使用X射线衍射的产品的结构特征.
主要成果:
- 一系列 dodecaalkoxy-closo-dodecaborate衍生物的成功合成.
- 为[closo-B12(OR) [12]2-.证明了两个可逆的,连续的单电子氧化过程.
- 确定用于氧化还原转换的最佳氧化和还原剂.
- 显著减少反应时间和提高效率,使用自闭槽条件实现.
- X射线衍射证实了由于Jahn-Teller扭曲的氧化物种的二和D3d对称的Ih对称性.
结论:
- 化[closo-B12(OH) [12]2-是一种可行的途径,可以产生多种多德卡基-克洛索-多德卡酸盐.
- 这些集群表现出可调节的氧化还原特性,使得可以接触到基离子和中性物种.
- 车条件提供了一种高效的方法来合成这些有价值的化合物.
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