• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Chemistry: A European journal >Enhanced Catalytic Activity and Unexpected Products from the Oxidation of Cyclohexene by Organic Nanoparticles of 5,10,15,20-Tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrinatoironACHTUNGTRENUNG(III) in Water by Using O2
【24h】

Enhanced Catalytic Activity and Unexpected Products from the Oxidation of Cyclohexene by Organic Nanoparticles of 5,10,15,20-Tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrinatoironACHTUNGTRENUNG(III) in Water by Using O2

机译：通过使用O2在水中对5,10,15,20-四-（2,3,4,5,6-五氟苯基）卟啉铁的有机纳米粒子氧化环己烯的催化活性和意外产物的合成

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The catalytic oxidation of alkenes by most iron porphyrins using a variety of oxygen sources, but generally not dioxygen, yields the epoxide with minor quantities of other products. The turnover numbers for these catalysts are modest, ranging from a few hundred to a few thousand depending on the porphyrin structure, axial ligands, and other reaction conditions. Halogenation of substituents increases the activity of the metalloporphyrin catalyst and/or makes it more robust to oxidative degradation. Oxidation of cyclohexene by 5,10,15,20-tetrakis-(2,3,4,5,6- pentafluorophenyl)porphyrinato iron- ACHTUNGTRENUNG(III), ([FeIIIACHTUNGTRENUNG(tppf20)]) and H2O2 is typical of the latter: the epoxide is 99% of the product and turnover numbers are about 350.[1–4] Herein, we report that dynamic organic nanoparticles (ONPs) of [FeIIIACHTUNGTRENUNG(tppf20)] with a diameter of 10 nm, formed by host–guest solvent methods, catalytically oxidize cyclohexene with O2 to yield only 2-cyclohexene- 1-one and 2-cyclohexene-1-ol with approximately 10-fold greater turnover numbers compared to the non-aggregated metalloporphyrin in acetonitrile/ methanol. These ONPs facilitate a greener reaction because the reaction solvent is 89% water and O2 is the oxidant in place of synthetic oxygen sources. This reactivity is unexpected because the metalloporphyrins are in close proximity and oxidative degradation of the catalyst should be enhanced, thus causing a significant decrease in catalytic turnovers. The allylic products suggest a different oxidative mechanism compared to that of the solvated metalloporphyrins. These results illustrate the unique properties of some ONPs relative to the component molecules or those attached to supports.
机译：大多数铁卟啉使用多种氧源（通常不是双氧源）催化氧化烯烃，生成的环氧化物和其他少量产物。这些催化剂的周转次数适中，取决于卟啉结构，轴向配体和其他反应条件，范围从几百到几千。取代基的卤化增加了金属卟啉催化剂的活性和/或使其对氧化降解更稳定。环己烯被5,10,15,20-四-（2,3,4,5,6-五氟苯基）卟啉氧化为铁-ACHTUNGTRENUNG（III），（[[FeIIIACHTUNGTRENUNG（tppf20）]）和H2O2的氧化：环氧化物占产物的99％，周转数约为350。[1-4]在此，我们报道了[FeIIIACHTUNGTRENUNG（tppf20）]的动态有机纳米颗粒（ONP），其直径为10 nm，是由主体–客体溶剂法，用O2催化氧化环己烯，仅生成2-环己烯-1-酮和2-环己烯-1-醇，与未聚集的金属卟啉在乙腈/甲醇中的转化率相比，大约高出10倍。这些ONP促进了绿色反应，因为反应溶剂是89％的水，而O2是代替合成氧源的氧化剂。该反应性是出乎意料的，因为金属卟啉非常接近并且应该增强催化剂的氧化降解，从而导致催化转化率显着降低。与溶剂化的金属卟啉相比，该烯丙基产物显示出不同的氧化机理。这些结果说明了某些ONP相对于组分分子或那些附着在载体上的独特性质。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号