• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Chemistry: A European journal >Reaction of [TpRh(C2H4)(2)] with Dimethyl Acetylenedicarboxylate: Identification of Intermediates of the [2+2+2] Alkyne and Alkyne-Ethylene Cyclo(co)trimerizations
【24h】

Reaction of [TpRh(C2H4)(2)] with Dimethyl Acetylenedicarboxylate: Identification of Intermediates of the [2+2+2] Alkyne and Alkyne-Ethylene Cyclo(co)trimerizations

机译：[TpRh（C2H4）（2）]与乙二甲酸二甲酯的反应：[2 + 2 + 2]炔和炔-乙烯环（共）三聚化中间体的鉴定

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 between the bis(ethylene) complex [TpRh(C2H4)(2)], 1, (Tp=hydrotris(pyrazolyl)borate), and dimethyl acetylenedicarboxylate (DMAD) has been studied under different experimental conditions. A mixture of products was formed, in which TpRh(I) species were prevalent, whereas the presence of trapping agents, like water or acetonitrile, allowed for the stabilization and isolation of octahedral TpRh(III) compounds. An excess of DMAD gave rise to a small amount of the [2+2+2] cyclotrimerization product hexamethyl mellitate (6). Although no catalytic application of 1 was achieved, mechanistic insights shed light on the formation of stable rhodium species representing the resting state of the catalytic cycle of rhodium-mediated [2+2+2] cyclo(co)trimerization reactions. Metallacyclopentene intermediate species, generated from the activation of one alkyne and one ethylene molecule from 1, and metallacyclopentadiene species, formed by oxidative coupling of two alkynes to the rhodium centre, are crucial steps in the pathways leading to the final organometallic and organic products.
机译：在不同的实验条件下，已经研究了双（乙烯）配合物[TpRh（C2H4）（2）]，1（Tp =氢三（吡唑基）硼酸酯）和乙炔二甲酸二甲酯（DMAD）之间的反应。形成了产物混合物，其中普遍存在TpRh（I）物质，而捕集剂（如水或乙腈）的存在则可以稳定和分离八面体TpRh（III）化合物。过量的DMAD产生了少量的[2 + 2 + 2]环三聚产物六甲基三氟甲磺酸盐（6）。尽管没有实现1的催化应用，但是机械学的见解揭示了稳定的铑物种的形成，该物种代表了铑介导的[2 + 2 + 2]环（共）三聚反应的催化循环的静止状态。由一个炔烃和一个乙烯分子从1活化而产生的金属环戊烯中间物质，以及两个炔烃与铑中心的氧化偶联形成的金属环戊二烯物质，是导致最终有机金属和有机产物的途径中的关键步骤。

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