高等学校化学学报

高等学校化学学报 ›› 1984, Vol. 5 ›› Issue (6): 869.

• 论文 • 上一篇    下一篇

过渡金属五卤苯基有机化合物的研究(Ⅱ)——五氯苯基镍化合物亲核取代反应动力学

陈荣悌1, 张启衍1, 王先红1, 王序昆2, 张正之2   

  1. 1. 南开大学化学系;
    2. 南开大学元素有机化学研究所
  • 收稿日期:1983-07-22 出版日期:1984-12-24 发布日期:1984-12-24

Study on the Organometallic Compounds of Transition Metals Containing Pentahaloaryl Ligands(Ⅱ)——The Kinetics and Mechanisms of Nucleophilic Substitution Reactions of Bis (diphenylalkylphosphine) pentachlo-RophenvInickeK (Ⅱ)Halides

Chen Rongti1, Zhang Qiyan1, Wang Xianhong1, Wang Xukun2, Zhang Zhengchi2   

  1. 1. Department of Chemistry, Tianjin;
    2. The Institute of Elerientoorgaic Chemistry, Naukai University, Tianjin
  • Received:1983-07-22 Online:1984-12-24 Published:1984-12-24

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摘要： 本文用分光光度法研究了双(二苯基烷基膦)合(五氯苯基)卤化镍(MX)与NO2-和CNS-在MeOH、EtOH和DMF溶剂中的亲核取代反应动力学.实验表明,反应遵循两项速率定律,即γ=(k1+k2[L])[MX].实验分别测定了不同温度下的速率常数k1、k2值及对应的活化参数△H≠和△S≠值.讨论了反应机理、溶剂效应,以及化合物中的不同烷基膦配体、不同离去基团和不同进入基团对反应速率的影响.

Abstract: The kinetics of nuclcophilic substitution reactions of bis(diphenyl-alkylphosphine) pentachlorophenylnickel (Ⅱ) halides with NO2- and SCN- in MeOH EtOH and DMF was studied by spectrophotometric method. The results indicated that the reactions followed a two-term reaction rate law, that is, r = (k1 + k2[L]) [complex], k1, and k2 values were determined at different temperatures and the corresponding activated thermodynamic parameters △H≠ and △S≠ were evalualed. Reaction mechanisms have been proposed and factors influencing the reaction rate such as solvent effect, nature of the leaving and entering groups, different alkyl groups in the phosphine ligand, etc, have been discussed.

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