高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

N-亚硝基吲哚系列化合物及其自由基负离子在乙腈介质中N—NO键断裂能的测定

李鑫, 朱晓晴, 王小小, 程津培   

  1. 南开大学化学系, 元素有机国家重点实验室, 天津 300071
  • 收稿日期:2007-05-18 修回日期:1900-01-01 出版日期:2007-12-10 发布日期:2007-12-10
  • 通讯作者: 程津培

Determination of N—NO Bond Dissociation Energies of N-Nitrosoindoles and Their Radical Anions in Acetonitrile

LI Xin, ZHU Xiao-Qing, WANG Xiao-Xiao, CHENG Jin-Pei*   

  1. The State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Nankai University, Tianjin 300071, China
  • Received:2007-05-18 Revised:1900-01-01 Online:2007-12-10 Published:2007-12-10
  • Contact: CHENG Jin-Pei

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摘要： 利用滴定量热技术并结合适当的热力学循环测定了乙腈溶液中7个取代的N-亚硝基吲哚化合物中N—NO键的异裂能和均裂能, 能量范围分别为206.1~246.2 kJ/mol和119.1~124.6 kJ/mol. 表明N-亚硝基吲哚均裂释放NO自由基(NO·)比异裂释放NO正离子(NO+)要容易得多, 通过热力学循环得到的相应自由基负离子中N—NO键的异裂能和均裂能的能量范围分别为25.5~34.4和5.0~40.5 kJ/mol, 表明所研究化合物的自由基负离子在室温下很不稳定.

关键词: N-亚硝基吲哚, N-亚硝基吲哚自由基负离子, N—NO键能, 滴定量热

Abstract: The heterolytic and homolytic N—NO bond dissociation energies of seven N-nitrosoindole derivatives were evaluated by using titration calorimetry and relative thermodynamic cycles. The energetic scales of the heterolytic and homolytic N—NO bond dissociation energies of N-nitrosoindoles cover the ranges from 206.1 to 246.2 kJ/mol and from 119.1 to 124.6 kJ/mol, respectively, which indicates that N-nitrosoindoles are much easier to release a NO radical(NO·) rather than a NO cation(NO+). The estimation of the heterolytic and homolytic(N—NO)-· bond dissociation energies of the N-nitrosoindoles radical anions gives the energetic ranges from 25.5 to 33.4 kJ/mol and from 5.0 to 40.5 kJ/mol for the(N—NO)-· bond homolysis and heterolysis, respectively, which means that N-nitrosoindole radical anions are unstable at room temperature.

Key words: N-Nitrosoindoles, Radical anions of N-nitrosoindoles, N—NO bond energy, Titration calorimetry

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