不饱和半夹芯式16e化合物Cp*Ir(S_2C_2B_(10)H_(10))与邻、间位取代苯基叠氮的反应性  

Reactivity of Unsaturated 16e Half-Sandwich Complex Cp*Ir(S_2C_2B_(10)H_(10))with ortho-and meta-Substituted Phenyl Azides

作　　者：钟伟[1,2] 燕红[2] 

机构地区：[1]嘉兴学院生物与化学工程学院,嘉兴314001 [2]南京大学配位化学国家重点实验室,南京210093

出　　处：《无机化学学报》2015年第7期1305-1314,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21301071)资助项目

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。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 recta-substituted phenyl azides were performed. Reaction of 1 with ortho- and recta-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. CCDC： 1046784, 2b; 1046785, 2c; 1046786, 2d; 1046787, 3b; 1046788, 3c; 1046789, 3d; 1046790, 7a; 1046791, 7b.

关 键 词：半夹芯式配合物 取代苯基叠氮 反应性 机理 

分 类 号：O614.825[理学—无机化学]