高等学校化学学报 ›› 1992, Vol. 13 ›› Issue (10): 1291.

• 论文 • 上一篇    下一篇

金属羰基化合物的氧原子转移反应——取代亚碘酰苯存在下Cr(CO)6的CO取代反应动力学研究

焦向东, 范文革, 高忆慈, 史启祯   

  1. 兰州大学化学系, 兰州, 730000
  • 收稿日期:1991-10-29 修回日期:1992-05-16 出版日期:1992-10-24 发布日期:1992-10-24
  • 通讯作者: 高忆慈
  • 基金资助:

    国家自然科学基金

Oxygen Atom Transfer Reactions of Metal Carbonyl Compounds——Kinetics of CO Substitution Reactions of Cr(CO)6 in the Presence of Substituted Iodosylbenzenes

JIAO Xiang-Dong, FAN Wen-Ge, GAO Yi-Ci, SHI Qi-Zhen   

  1. Department of Chemistry, Lanzhou University, Lanzhou 730000
  • Received:1991-10-29 Revised:1992-05-16 Online:1992-10-24 Published:1992-10-24

摘要: 在取代亚碘酰苯存在下,研究了Cr(CO)6与外来配体L(L=CH3CN、PPh3)间的羰基取代反应动力学.结果表明,该试剂的空间效应加快了反应速度,其活性顺序为:邻位取代>间位取代>对位取代>未取代;不同基团的对位取代亚碘酰苯的电子效应与氧原子转移速度之间呈良好的线性关系.吸电子基促进反应,在位阻相近的情况下,取代亚碘酰苯的活性随I—O键强减小而增大.

关键词: 取代亚碘酰苯, 六羰基铬, 氧原子转移, 动力学

Abstract: The kinetic data are reported for the reactions between Cr(CO)6 and the entering lin-gands L(where L=CH3CN,PPh3) in the presence of substituted iodosylbenzenes R-C6H4IO to form Cr(CO)5L.The results indicate that the steric hindrance of substituents of R-C6H4IO increases the rate of the reactions,the reactivities decreases in the order;o-substituted>m-substi-tuted>p-substituted>unsubstituted.There is a good linear correlation between the rate of O-a-torn transfer reactions and the electronic factors of p-substituted iodosylbenzenes,and the electron-withdrawing substituents make the reaction faster,the reactivities of R-C6H4IO increase with weakening the I-Obond strengths at the similar steric hindrance.

Key words: Substituted iodosylbenzenes, Hexacarbonyl chromium, Oxygen atom transfer, Kinetics

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