物理化学学报 >> 1991, Vol. 7 >> Issue (05): 518-523.doi: 10.3866/PKU.WHXB19910502

研究论文 上一篇    下一篇

溶液中(RC2R')Co(CO)(PR″3)2的配体PR″3之间的交换作用——三跳动力学模型

孟庆金; 孙守恒; 朱丹红; 陈卫兵; P.H.Rieger   

  1. 南京大学配位化学研究所,南京 210008; Chemistry Department, Brown University, Providence, RI 02912
  • 收稿日期:1990-03-27 修回日期:1990-11-06 发布日期:1991-10-15
  • 通讯作者: 孟庆金

Chemical Exchange of Ligand PR″3 of (RC2R)Co(CO)(PR″3)2 IN SOLUTION——TRIPLE-JUMP KINETIC MODEL

Meng Qing-Jin; Sun Shou-Heng; Zhu Dan-Hong; Chen Wei-Bing; P.H.Rieger   

  1. Coordination Chemistry Institute, Nanjing University, Nanjing 210008; Chemistry Department, Brown University, Providence, RI 02912
  • Received:1990-03-27 Revised:1990-11-06 Published:1991-10-15
  • Contact: Meng Qing-Jin

摘要: 本文成功地运用了三跳动力学模型,通过相关函数和超精细分裂常数的关系, 推出了电子自旋共振波谱的线宽与基本线宽T_(2,0)~(-1)、溶液中各种异构体的超精细分裂常数、配体的交换寿命等之间的关系。求出了在290 K温度下(Ph_2C_2)Co(CO)[P(OEt)_3]_2的THF溶渡中P(OEt)_3配体的交换寿命是5.6×10~(-11)秒。

关键词: 钴配合物, 配体交换, 三跳模型

Abstract: This paper described a detailed theoretical analysis of ESR spectrum line width of the cobalt complex (RC_2R/)Co(CO)(PR"_3)_2 in solution. Triple-jump kinetic model was first used in the Trans-Cis isomerism of the complex.A formula concerning ESR line width as a function of the basic line width T_(20)~(-1), hyperfine splitting constants of all isomers in solution, and lifetime of the exchange of ligand PR"_3 were suggested on the relationship between the correlation function and the hyperfine splitting constant. The calculated, exchange lifetime of the ligand P(OEt)_3 in the title complex (Ph_2C_2)Co(CO)[P(OEt)_3]_2 at 290 K is 5.6×10~(-11) s.

Key words: Cobalt complex, Ligand exchange, Tripe-jump model