...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Tellurorhodamine photocatalyzed aerobic oxidation of organo-silanes and phosphines by visible-light
【24h】

Tellurorhodamine photocatalyzed aerobic oxidation of organo-silanes and phosphines by visible-light

机译：通过可见光通过碲催化剂的有机硅烷和磷酸的有氧氧化

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

Tellurorhodamine, 9-mesityl-3,6-bis(dimethylamino)telluroxanthylium hexafluorophosphate (1), photocatalytically oxidizes aromatic and aliphatic silanes and triphenyl phosphine under mild aerobic conditions. Under irradiation with visible light, 1 can react with self-sensitized O-1(2) to generate the active telluroxide oxidant (2). Silanes are oxidized to silanols and triphenyl phosphine is oxidized to triphenyl phoshine oxide either using 2, or 1 with aerobic irradiation. Kinetic experiments coupled with a computational study elucidate possible mechanisms of oxidation for both silane and phosphine substrates. First-order rates were observed in the oxidation of triphenyl phosphine and methyldiphenyl silane, indicating a substitution like mechanism for substrate binding to the oxidized tellurium(iv). Additionally, these reactions exhibited a rate-dependence on water. Oxidations were typically run in 50:50 water/methanol, however, the absence of water decreased the rates of silane oxidation to a greater degree than triphenyl phosphine oxidation. Parallel results were observed in solvent kinetic isotope experiments using D2O in the solvent mixture. The rates of oxidation were slowed to a greater degree in silane oxidation by 2 (k(H)/k(D) = 17.30) than for phosphine (k(H)/k(D) = 6.20). Various silanes and triphenyl phosphine were photocatalytically oxidized with 1 (5%) under irradiation with warm white LEDs using atmospheric oxygen as the terminal oxidant.
机译：Tellurorhodamine，9-三甲苯基-3,6-双（二甲基氨基）六氟磷酸telluroxanthylium（1），光催化氧化温和的需氧条件下的芳族和脂族硅烷和三苯基膦。下用可见光照射时，1可与自增感O-1（2）反应以产生活性telluroxide氧化剂（2）。硅烷被氧化成硅醇基和三苯基膦被氧化为三苯基氧化phoshine或者使用2，或1与有氧照射。动力学实验加上氧化的两种硅烷和磷化氢基板的计算研究阐发可能机制。在三苯基膦及甲基二苯基硅烷的氧化观察到一阶速率，表示相同的机构，用于底物结合到氧化碲（Ⅳ）的取代。此外，这些反应表现出对水的速率依赖性。氧化是典型在50:50的水/甲醇运行，然而，不存在水降低硅烷氧化速率比三苯膦氧化更大的程度。平行导致在溶剂混合物中使用D 2 O溶剂动力学同位素实验中观察到。氧化的速率通过2（K（H）/ K（d）= 17.30）比膦（K（H）/ K（d）= 6.20）减慢至在硅烷氧化更大的程度。各种硅烷和三苯基膦的光催化用1（5％），使用大气中的氧作为氧化剂终端暖白色LED照射下氧化。

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