| 不饱和半夹芯式16e化合物Cp*Ir(S2C2B10H10)与邻、间位取代苯基叠氮的反应性 |
| Reactivity of Unsaturated 16e Half-Sandwich Complex Cp*Ir(S2C2B10H10) with ortho- and meta-Substituted Phenyl Azides |
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| 摘要: 考虑取代基的位置和电子效应对反应体系的影响, 本文系统地研究了16e化合物Cp*Ir(S2C2B10H10) (1)与邻、间位取代苯基叠氮的反应。研究结果表明:与邻、间位取代苯基叠氮反应均生成苯环邻位碳发生C-H 活化形成C-S 键的金属配合物。这些配合物通过核磁(1H、11B、13C)、红外、质谱、元素分析和单晶结构解析进行了全面地表征。在光照反应结果的基础上, 提出了形成这类产物的自由基机理。 |
| 关键词: 半夹芯式配合物 取代苯基叠氮 反应性 机理 |
| 基金项目: 国家自然科学基金(No.21301071)资助项目。 |
| Abstract: To test the influence of the position and electronic effect of the substituted group on the reaction system, detailed studies on the reactivity of unsaturated 16e half-sandwich complex Cp*Ir(S2C2B10H10) (1) with ortho- and meta-substituted phenyl azides were performed. Reaction of 1 with ortho- and meta-substituted phenyl azides led to the formation of metal complexes in which C-H activation at ortho-position of aryl ring happened to construct a new C-S bond. These complexes were fully characterized by NMR (1H, 11B, 13C), FTIR, MS, elemental analysis and single crystal X-ray diffraction. Basing on the results of the same reaction system with irradiation, the radical mechanism for the formation of these complexes was proposed. |
| Keywords: half-sandwich complex substituted phenyl azide reactivity mechanism |
| 投稿时间：2015-02-02 修订日期：2015-06-02 |
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| 钟伟,燕红.不饱和半夹芯式16e化合物Cp*Ir(S2C2B10H10)与邻、间位取代苯基叠氮的反应性[J].无机化学学报,2015,31(7):1305-1314. |
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