| 半夹芯16电子化合物CpCo(S2C2B10H10)与乙炔基二茂铁在甲醇中的反应性 | |
| Reactivity of the Half-Sandwich 16e Compound CpCo(S2C2B10H10) with Ethynylferrocene in Methanol | |
| 摘要: 半夹芯16电子化合物CpCo(S2C2B10H10) (1)(Cp:cyclopentadienyl)与过量乙炔基二茂铁(FcC≡CH)(Fc:ferrocenyl)在甲醇中反应，分离得到了化合物(CHCFc)(CH=CFc)(S2C2B9H10) (8)和2个乙炔基二茂铁环三聚产物1,2,4-三二茂铁基苯和1,3,5-三二茂铁基苯。在8中，2个乙炔基二茂铁分子以“头对头”方式聚合连接到CpCo(S2C2B10H10)分子中的2个S原子上，导致CpCo结构单元的丢失。碳硼烷笼体B(3)位上的BH键发生活化，该B原子与1个乙炔基二茂铁分子的乙炔基末端C原子连接生成C-B键；同时，B(6)位的BH碎片在甲醇作用下失去，从而closo-C2B10闭式结构转变成nido-C2B9巢式结构。化合物 8用单晶 X-射线衍射分析方法进行了表征。 | |
| 关键词: 半夹芯 碳硼烷 乙炔基二茂铁 甲醇 反应性 | |
| 基金项目: | |
| Abstract: The half-sandwich 16e cobalt compound CpCo(S2C2B10H10) (1) (Cp: cyclopentadienyl) reacted with excess ethynylferrocene (FcC≡CH) (Fc: ferrocenyl) in methanol to give complex 8 and two ethynylferrocene cyclotrimerization compounds: 1,2,4-triferrocenylbenzene and 1,3,5-triferrocenylbenzene. In 8, two ethynylferrocene molecules are coupled in the head-to-head way and linked to the two sulfur atoms of the CpCo(S2C2B10H10) molecule, leading to loss of the CpCo unit. The BH bond at B(3) site of the carborane cage has been activated and the boron atom was connected to the terminal carbon of one alkyne to generate a C-B bond. Whereas the BH apex at the B(6) site has been lost in the presence of methanol, as a result, the closo-C2B10 carborane cage was converted into a nido-C2B9 carborane cage. The complex 8 has been characterized by single-crystal X-ray diffraction analysis. CCDC: 808991. | |
| Keywords: half-sandwich carborane ethynylferrocene methanol reactivity | |
| 摘要点击次数: 1744 | |
| 全文下载次数: 1579 | |
| 叶红德,白文娟,郑大贵,胡久荣,彭化南,燕 红.半夹芯16电子化合物CpCo(S2C2B10H10)与乙炔基二茂铁在甲醇中的反应性[J].无机化学学报,2012,28(8):1535-1540. | |
| 查看全文 查看/发表评论 下载PDF阅读器 | |
| Support information: | |
|
| |
|
| |
|
| |