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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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【作者】 钟伟燕红

【Author】 ZHONG Wei;YAN Hong;College of Biological,Chemical Sciences and Engineering,Jiaxing University;State Key Laboratory of Coordination Chemistry,Nanjing University;

【机构】 嘉兴学院生物与化学工程学院南京大学配位化学国家重点实验室

【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。

【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 16 e 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,11 B,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.

【基金】 国家自然科学基金(No.21301071)资助项目
  • 【文献出处】 无机化学学报 ,Chinese Journal of Inorganic Chemistry , 编辑部邮箱 ,2015年07期
  • 【分类号】O641.4
  • 【下载频次】53
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