期刊文献+

过渡金属离子与烷烃反应机理的理论研究──镍离子(~2D)与丙烷反应中氢分子的还原消除机理

Theoretical Studies of the Mechanism and Energetics for the Reactions of Transition Metal Ions with Alkanes──H_2 Elimination Mechanism in the Reaction of Ni^+(~2D) with Propane
下载PDF
导出
摘要 以Ni+与C3H8反应作为过渡金属离子与烷烃反应的范例体系,用B3LYP密度泛函方法计算了[Ni,C3,H8]+基态势能面上各驻点的构型、频率和能量,结果表明,该反应的H2分子消除需经历两个基元步骤,即Ni+ 首先插入一级或二级C- H键,然后经H转移过渡态异构化为较稳定的中间体,继而解离产生H2 分子.计算的反应热为 142.28 kJ/mol,与相应的实验值(127.85 kJ/mol)符合较好. Abstract The reaction of Ni+ with propane have been studied extensively by using density functional theory , and the detailed information regarding the mechanism and energetics of H2 elimination on the potential energy surface of [Ni,C3,H8]+ have been obtained at B3LYP/6-311 + +G(3df/,3pd) level. Both the initial primary or secondary C桯 bond activations in propane mediated by Ni+ in the reaction of Ni+ with propane can result in the H2 elimination from Ni(C3H8) + . Five intermediates, two C桯 bond activation transition states and three H-shift transition states are located on this potential energy surface. The heat ofreaction for Ni++C3H8 Ni(C3H6)++H2 is calculated to be 142. 28 kj/mol. This result is in goodagreement with the experimental finding, a value of 127. 85 kJ/mol at 0 K.
出处 《高等学校化学学报》 SCIE EI CAS CSCD 北大核心 2002年第5期876-879,共4页 Chemical Journal of Chinese Universities
基金 山东省自然科学基金重大项目(批准号:Z2000B02)资助.
关键词 过渡金属离子 烷烃 反应机理 密度泛函理论 镍离子 丙烷 氢分子 还原消除机理 Transition metal ion Alkanes Reaction mechanism Density functional theory
  • 相关文献

参考文献13

  • 1Allison J., Freas R. B., Ridge D. P.. J. Am. Chem. Soc.[J], 1979, 101: 1 332-1 333
  • 2Armentrout P. B.. Top. Organomet. Chem.[J], 1999, 4: 1-45
  • 3Martinho S. J. A., Beauchamp J. L.. Chem. Rev.[J], 1990, 90: 629-688
  • 4Eller K., Schwarz H.. Chem. Rev.[J], 1991, 91: 1 121-1 177
  • 5Tonkyn R., Ronan M., Weisshaar J. C.. J. Phys. Chem.[J], 1988, 92: 92-102
  • 6Ziegler T.. Chem. Rev.[J], 1991, 91: 651-667
  • 7Andzelm J., Wimmer E.. J. Chem. Phys.[J], 1992, 96: 1 280-1 289
  • 8莫依,黎乐民.密度泛函计算条件对结果精度的影响[J].高等学校化学学报,2001,22(1):81-85. 被引量:17
  • 9ZHANGDong-Ju(张冬菊) LIUCheng-Bu(刘成卜).化学学报,2001,59:1406-1412.
  • 10Raghavachari K., Trucks G. W.. J. Chem. Phys.[J], 1989, 91: 1 062-1 065

二级参考文献3

共引文献16

相关作者

内容加载中请稍等...

相关机构

内容加载中请稍等...

相关主题

内容加载中请稍等...

浏览历史

内容加载中请稍等...
;
使用帮助 返回顶部