...
  • 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 >Theoretical study of reaction pathways for the rhodium phosphine-catalysed borylation of C-H bonds with pinacolborane
【24h】

Theoretical study of reaction pathways for the rhodium phosphine-catalysed borylation of C-H bonds with pinacolborane

机译：铑膦催化频哪醇硼烷C-H键硼化反应机理的理论研究

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 reaction mechanism of the rhodium-phosphine catalysed borylation of methyl-substituted arenes using pinacolborane (HBpin) has been investigated theoretically using DFT calculations at the B3PW91 level. Factors affecting selectivity for benzylic vs. aromatic C-H bond activation have been examined. It was found that [Rh(PR_3)_2(H)] is the active species which oxidatively adds the C-H bond leading to an eta~3-benzyl complex which is the key to determining the unusual benzylic regioselectivity observed experimentally for this catalyst system. Subsequent reaction with HBpin leads to a [Rh(PR_3)_2(eta~3-benzyl)(H)(Bpin)] complex from which B-C reductive elimination provides product and regenerates the catalyst. The electrophilic nature of the boryl ligand assists in the reductive elimination process. In contrast to Ir(L)_2(boryl)_3-based catalysts, for which Ir(III)-Ir(v) cycles have been proposed, the Rh(I)-Rh(III) cycle is operating with the system addressed herein.
机译：理论上使用DFT计算在B3PW91水平上研究了铑-膦催化的频哪酚硼烷（HBpin）甲基取代的芳烃的硼化反应。已经研究了影响苄基与芳族C-H键活化选择性的因素。发现[Rh（PR_3）_2（H）]是氧化加成C-H键导致η〜3-苄基络合物的活性物质，这是确定对该催化剂体系实验观察到的异常苄基区域选择性的关键。随后与HBpin的反应导致生成[Rh（PR_3）_2（η3-苄基）（H）（Bpin）]络合物，从该络合物中进行B-C还原消除可提供产物并再生催化剂。硼基配体的亲电子性质有助于还原消除过程。与已提出Ir（III）-Ir（v）循环的Ir（L）_2（硼基）_3基催化剂相反，Rh（I）-Rh（III）循环在本文所述系统下运行。

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