| 袁润泽,金国新.含有碳硼烷的有机金属大环化合物[J].井冈山大学自然版,2025,46(3):21-30 |
| 含有碳硼烷的有机金属大环化合物 |
| HALF-SANDWICH METALLACYCLES SUPPORTED BY O-CARBORANE LIGANDS |
| 投稿时间：2025-03-02 修订日期：2025-04-16 |
| DOI：10.3969/j.issn.1674-8085.2025.03.004 |
| 中文关键词: 碳硼烷 半夹心络合物 1,1-二硫醇盐络合物 金属环 三氯锡配合物 |
| 英文关键词: carborane half-sandwich complex 1,1-dithiolate complex metallacycles trichlorostannyl complex |
| 基金项目:The National Science Foundation of China(22031003,21720102004) and the Shanghai Science Technology Committee (19DZ2270100) |
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| 中文摘要: |
| 研究描述了四个半夹心铱铑配合物的合成和表征，它们的合成基于Cp*MCl(o-C2B10H11CS2) (配合物1a(Ir)和1b(Rh)) (Cp* = η5- C5Me5)和相应的还原剂之间的反应。其中，一种具有敞开式立方烷结构的配合物[Cp*Ir(o-C2B10H11CHS2)]2 (配合物2)通过1a和硼氢化锂或硼氢化钠的还原反应制备；一种三核有机金属大环配合物[Cp*Ir(o-C2B10H10CS2)]3 (配合物3)通过1a和BH3·THF在甲苯中的共热解反应制备，其铑类似物[Cp*Ir(o-C2B10H10CS2)]3 (配合物4)可通过三苯基铋协同下1b的脱氯反应制备；一种铱和锡原子之间直接金属成键的配合物Cp*Ir(o-C2B10H11CS2) (SnCl3) (配合物5)则通过1a和氯化亚锡之间的氧化加成反应制备。对于这些新配合物，实验中使用了包括X射线单晶衍射、核磁共振和元素分析在内的方法的充分表征。 |
| 英文摘要: |
| Herein, we describe the synthesis and characterization of four complexes containing half-sandwich iridium metal-corner which were obtained through the interaction between known complexes Cp*MCl(o-C2B10H11CS2) (M = Ir/Rh, Complex 1a and 1b) and corresponding reagents. An incomplete cubane-like complex [Cp*Ir(o-C2B10H11CHS2)]2 (Complex 2) has been prepared through the reaction between 1a and LiBH4 or NaBH4. Co-thermolysis between 1a and BH3·THF in toluene produces a trimer metallacycle complex [Cp*Ir(o-C2B10H10CS2)]3 (Complex 3), while its rhodium analogue [Cp*Rh(o-C2B10H10CS2)]3 (Complex 4) can be prepared through BiPh3-assisted dechlorination reaction of 1b. Furthermore, the oxidative addition reaction of 1a towards SnCl2 generates a mononuclear complex Cp*Ir(SnCl3)(o-C2B10H11CS2) (Complex 5) with a direct Sn-Ir bond. These complexes have been characterized, including X-Ray single crystal diffraction, NMR spectroscopy and elemental analysis methods. |
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