【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。更多还原

【Abstract】 The reaction of the 16e half-sandwich complex CpCo(S 2 C 2 B 10 H 10)(Cp: cyclopentadienyl)(1) and the alkyne HC ≡CC(O)Fc(Fc: ferrocenyl) in a molar ratio of 1 ∶1 leads to CpCo(S 2 C 2 B 10 H 9)(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(S 2 C 2 B 10 H 8)(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.更多还原