| 半夹芯16电子化合物CpCo(S2C2B10H10)中B(3,6)位的选择性分步取代反应(英文) |
| Selective Stepwise Substitution in B(3,6) Positions of 16e Half-Sandwich Complex CpCo(S2C2B10H10) |
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| 摘要: 16e半夹芯化合物CpCo(S2C2B10H10)(Cp：cyclopentadienyl) (1)与炔烃HC≡CC(O)Fc(Fc：ferrocenyl)在物质的量之比为1∶1时反应生成化合物CpCo(S2C2B10H9)(CH=CHC(O)Fc) (2)。在化合物2中，一分子HC≡CC(O)Fc偶合到原料化合物1的碳硼烷笼子的B(3)位点，导致B(3)位的氢原子迁移到炔烃的内部碳原子上形成烯烃取代基。2能继续与另外一分子HC≡CC(O)Fc反应，生成B-双取代产物CpCo(S2C2B10H8)(CH=CHC(O)Fc)2(3)。3仍然是1个16e化合物，并且在B(3，6)位点有2个反式烯烃取代基CH=CHC(O)Fc。在过量炔烃存在情况下，该反应生成化合物3及炔烃环三聚产物1，3，5-{HC=CC(O)Fc}3(4)。化合物2、3、4用红外，核磁，元素分析，质谱和单晶X-射线衍射分析等方法进行了表征。 |
| 关键词: 过渡金属 碳硼烷 B-H键活化 晶体结构 |
| 基金项目: |
| Abstract: The reaction of the 16e half-sandwich complex CpCo(S2C2B10H10) (Cp: cyclopentadienyl) (1) and the alkyne HC≡CC(O)Fc (Fc: ferrocenyl) in a molar ratio of 1∶1 leads to CpCo(S2C2B10H9)(CH=CHC(O)Fc) (2) in which the alkyne is coupled to the B(3) site of the carborane cage thus resulting in the transferring hydrogen of B(3)-H to the internal carbon of the alkyne to form a olefinic substituent CH=CHC(O)Fc. 2 could further react with a second HC≡CC(O)Fc to generate a B-disubstituted product CpCo(S2C2B10H8)(CH=CHC(O)Fc)2(3). 3 is still a 16e compound with two CH=CHC(O)Fc olefinic substituents in E/E configurations at the B(3,6) sites. In the presence of excess alkyne, the reaction leads to 3 and the alkyne cyclotrimerization product 1,3,5-{HC=CC(O)Fc}3(4). Complexes 2, 3, 4 have been characterized by IR, NMR, elemental analysis, mass spectrometry and single-crystal X-ray diffraction analysis. CCDC: 813827, 2; 813828, 3; 802195, 4. |
| Keywords: transition metal carborane B-H activation crystal structure |
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| 叶红德,蒋其柏,解铭时,丁冠宇,李一志,燕 红.半夹芯16电子化合物CpCo(S2C2B10H10)中B(3,6)位的选择性分步取代反应(英文)[J].无机化学学报,2011,27(8):1601-1606. |
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