| 半夹芯16电子化合物CpCo(S_2C_2B_(10)H_(10))与乙炔基二茂铁在甲醇中的反应性 |
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| 引用本文： | 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(S_2C_2B_(10)H_(10))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. |
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| 作者姓名： | 叶红德 白文娟 郑大贵 胡久荣 彭化南 燕 红 |
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| 作者单位： | 1. 上饶师范学院江西省普通高校应用有机化学重点实验室,上饶师范学院化学化工学院,上饶334001
2. 南京大学化学化工学院,南京,210093 |
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| 基金项目： | 江西省普通高校重点实验室科技计划项目，江西省教育厅科技项目，江西省教育厅青年科学基金项目，教育部第四批高等学校特色专业建设点资助项目，教育部博士点基金 |
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| 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。
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| 关 键 词： | 半夹芯 碳硼烷 乙炔基二茂铁 甲醇 反应性 |
Reactivity of the Half-Sandwich 16e Compound CpCo(S2C2B10H10) with Ethynylferrocene in Methanol |
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| YE Hong-De,BAI Wen-Juan,ZHENG Da-Gui,HU Jiu-Rong,PENG Hua-Nan and YAN Hong.Reactivity of the Half-Sandwich 16e Compound CpCo(S2C2B10H10) with Ethynylferrocene in Methanol[J].Chinese Journal of Inorganic Chemistry,2012,28(8):1535-1540. |
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| Authors: | YE Hong-De BAI Wen-Juan ZHENG Da-Gui HU Jiu-Rong PENG Hua-Nan and YAN Hong |
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| Institution: | Key Laboratory of Applied Organic Chemistry, Higher Institutions of Jiangxi Province, School of Chemistry and Chemical Engineering, Shangrao Normal University, Shangrao, Jiangxi 334001, China,School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China,Key Laboratory of Applied Organic Chemistry, Higher Institutions of Jiangxi Province, School of Chemistry and Chemical Engineering, Shangrao Normal University, Shangrao, Jiangxi 334001, China,Key Laboratory of Applied Organic Chemistry, Higher Institutions of Jiangxi Province, School of Chemistry and Chemical Engineering, Shangrao Normal University, Shangrao, Jiangxi 334001, China,Key Laboratory of Applied Organic Chemistry, Higher Institutions of Jiangxi Province, School of Chemistry and Chemical Engineering, Shangrao Normal University, Shangrao, Jiangxi 334001, China and School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China |
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| 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. |
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| Keywords: | half-sandwich carborane ethynylferrocene methanol reactivity |
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