• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Study of the Mechanism of Hydrogenation of Side-On Coordinated Dinitrogen Activated by Zr Binuclear Complexes([eta_5-C_5Me_4H)_2Zr]_2(mu_2,eta~2,eta~2-N_2))
【24h】

Theoretical Study of the Mechanism of Hydrogenation of Side-On Coordinated Dinitrogen Activated by Zr Binuclear Complexes([eta_5-C_5Me_4H)_2Zr]_2(mu_2,eta~2,eta~2-N_2))

机译：Zr双核配合物（[eta_5-C_5Me_4H）_2Zr] _2（mu_2，eta〜2，eta〜2-N_2）活化的侧配位二氢加氢机理的理论研究

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 reduction of dinitrogen coordinated side-on to a binuclear Zr complex,([eta_5-C_5Me_4H)_2Zr]_2(mu_2,eta~2,eta~2-N_2))(T1),was investigated theoretically using a model complex,([eta_5-C_5Me_4H)_2Zr]_2(mu_2,eta~2,eta~2-N_2))(A1),employing density functional theory calculations.The effectiveness of A1 in describing Tl was confirmed by comparing the structures,distributions of charge,and frontier molecular orbitals.Our calculations showed that A1 has a twisted structure,resembling that of Tl,which results in similar properties.The calculations for A1 and its derivatives on H2 addition clearly explain the reaction mechanism and the reaction path that Tl follows,as well as the experimentally required reaction conditions.The immediate reaction of the first and second H_2 additions produces([eta_5-C_5Me_4H)_2Zr]_2(mu_2,eta~2,eta~2-N_2H_2))(T2),and this is explained by the barrier heights of the reaction,which were calculated to be 20.4 and 10.9 kcal/mol,respectively.The latter barrier was below that of Al + 2H_2.Complex T2 may be the initial complex for further H_2 addition under proper conditions,or it could lose one H_2 molecule followed by H migration from the Zr site to the N site.Both reactions are expected to occur,because of the closeness of the barrier heights(25.1 and 36.5 kcal/mol,respectively).Gentle warming is required for further H_2 additions,which can be understood from the energetics as well.The high reactivity of Tl with H_2 has been discussed by the comparison of the calculation of Al and another complex with different ligands,presenting an interesting indication on the effects of the ligands.These theoretical results and discussion explaining the experiment should provide insight into the nature of the hydrogenation mechanism.
机译：从理论上研究了将双氮侧向还原成双核Zr络合物[[eta_5-C_5Me_4H）_2Zr] _2（mu_2，eta〜2，eta〜2-N_2）（T1）的反应机理。模型[[eta_5-C_5Me_4H）_2Zr] _2（mu_2，eta〜2，eta〜2-N_2））（A1），采用密度泛函理论计算。计算表明，A1具有扭曲的结构，类似于T1，具有相似的性质。A1及其衍生物在H2加成上的计算清楚地说明了反应机理和反应路径。遵循T1以及实验所需的反应条件。第一次和第二次H_2加成的立即反应产生（[eta_5-C_5Me_4H）_2Zr] _2（mu_2，eta〜2，eta〜2-N_2H_2））（T2），这可以通过反应的势垒高度来解释，分别为20.4和10.9 kcal / mol后面的障碍低于Al + 2H_2。复合物T2可能是在适当条件下进一步添加H_2的初始复合物，或者它可能失去一个H_2分子，然后H从Zr位点迁移到N位点。由于势垒高度的接近性（分别为25.1和36.5 kcal / mol），预计会发生。进一步添加H_2需要进行温和的加热，这从能量学上也可以理解。Tl与H_2的高反应性通过比较铝和具有不同配体的另一种配合物的计算，讨论了这一点，为配体的作用提供了有趣的指示。

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