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

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。

Reactivity of Unsaturated 16e Half-Sandwich Complex Cp*Ir(S2C2B10H10) with ortho- and meta-Substituted Phenyl Azides

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.