...
首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Mechanistic examination of aerobic Pt oxidation: insertion of molecular oxygen into Pt-H bonds through a radical chain mechanism
【24h】

Mechanistic examination of aerobic Pt oxidation: insertion of molecular oxygen into Pt-H bonds through a radical chain mechanism

机译:有氧Pt氧化的机理检查:通过自由基链机制将分子氧插入Pt-H键

获取原文
获取原文并翻译 | 示例
           

摘要

DFT calculations were performed in an effort to evaluate the mechanism of O-2 insertion into the Pt-H bond of Tp(Me2)Pt(IV)Me(2)H catalyzed by AIBN or light. Results are consistent with a radical chain mechanism involving H-center dot loss to form a Pt-III center dot species followed by addition of O-2 to form (PtOO center dot)-O-III. Subsequent radical propagation involving this (PtOO center dot)-O-III species and an additional equivalent of the Pt-IV starting material result in the formation of the observed (PtOOH)-O-IV and regeneration of the Pt-III center dot. In addition examination of the reaction between AIBN and the Pt-IV hydroperoxo product demonstrates that radical initiation reactions involving the product occur with a lower barrier than with the initial starting material supporting the idea of autoacceleration in this reaction. Other possible mechanisms were examined in an effort to understand the limited reactivity reported in the absence of light or radical initiators. TDDFT calculations were performed in an effort to understand the reported parallel photo-induced reaction. These calculations found the reactant to be transparent in the relevant light range. An experimental UV-Vis spectrum was obtained and is in agreement with the calculations.
机译:进行DFT计算是为了评估O-2插入AIBN或光催化的Tp(Me2)Pt(IV)Me(2)H的Pt-H键中的机理。结果与自由基链机制一致,自由基链机制涉及H中心点损失形成Pt-III中心点物质,然后添加O-2形成(PtOO中心点)-O-III。随后的自由基传播涉及该(PtOOH中心点)-O-III物质和另一等价的Pt-IV起始材料,导致形成观察到的(PtOOH)-O-IV和Pt-III中心点的再生。另外,对AIBN和Pt-IV氢过氧产物之间的反应的检查表明,涉及产物的自由基引发反应发生的势垒比初始原料低,这支持了该反应中自动加速的想法。为了了解在没有光或自由基引发剂的情况下报道的有限反应性,研究了其他可能的机制。为了理解所报道的平行光诱导反应,进行了TDDFT计算。这些计算发现反应物在相关的光范围内是透明的。获得了实验紫外-可见光谱,与计算结果一致。

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