...
  • 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 >New insight into the role of a base in the mechanism of imine transfer hydrogenation on a Ru(ii) half-sandwich complex
【24h】

New insight into the role of a base in the mechanism of imine transfer hydrogenation on a Ru(ii) half-sandwich complex

机译：对Ru（ii）半三明治复合物上亚胺转移加氢机理中碱作用的新见解

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

Asymmetric transfer hydrogenation (ATH) of cyclic imines using [RuCl(η~6-p-cymene)TsDPEN] (TsDPEN = N-tosyl-1,2- diphenylethylenediamine) was tested with various aliphatic (secondary, tertiary) and aromatic amines employed in the HCOOH-base hydrogen donor mixture. Significant differences in reaction rates and stereoselectivity were observed, which pointed to the fact that the role of the base in the overall mechanism could be more significant than generally accepted. The hydrogenation mixture was studied by nuclear magnetic resonance (NMR), Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and vibrational circular dichroism (VCD) with infrared spectroscopy. The results suggested that the protonated base formed an associate with the active ruthenium-hydride species, most probably via a hydrogen bond with the sulfonyl group of the complex. It is assumed that the steric and electronic differences among the bases were responsible for the results of the initial ATH experiments.
机译：使用[RuCl（η〜6-p-cymene）TsDPEN]（TsDPEN = N-甲苯磺酰基-1,2-二苯基乙二胺）对环亚胺的不对称转移氢化（ATH）进行了测试，并采用了各种脂肪族（仲，叔）胺和芳香族胺在HCOOH基氢供体混合物中观察到反应速率和立体选择性方面的显着差异，这表明碱基在整个机理中的作用可能比通常所接受的更为重要。通过核磁共振（NMR），傅立叶变换离子回旋共振质谱（FT-ICR MS）和振动圆二色性（VCD）和红外光谱研究了氢化混合物。结果表明，质子化的碱与活性的氢化钌物质形成缔合体，最有可能通过与配合物的磺酰基的氢键形成。假定碱基之间的空间和电子差异是最初ATH实验结果的原因。

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