| 钴(Ⅲ)催化CpCoS2C2B10H10分子内B(3)/B(6)位和Cp配体偶联 | |
| Cobalt(Ⅲ)-Mediated Intramolecular Coupling of B(3)/B(6) in CpCoS2C2B10H10 with Cp Ligand | |
| 摘要: 半夹芯16e化合物CpCoS2C2B10H10(Cp:cyclopentadienyl) (1)与HC≡CCO2Me在2-甲基二硫代丙酸存在下反应生成化合物{(C5H4CoS2C2B9H9)(CH=CHCO2Me)(Me2C=CS2H)} (2)和(Me2C=CS2H)3Co (3)。在化合物2中, 原料化合物1中的一个S-Co键断裂, 该S原子与一分子HC≡CCO2Me末端炔基碳原子连接。Co原子与2-甲基二硫代丙酸的S原子连接成键, 2-甲基二硫代丙酸分子中的SH基团与Co原子通过配位键相连;同时, Cp环的一个碳原子与碳硼烷笼体的B(3)/B(6)位相连, 该B(3)/B(6)位的氢原子迁移到炔烃HC≡CCO2Me的内部炔基碳原子上形成反式烯键。3个2-甲基二硫代丙酸分子中的3个S原子分别与1中的Co原子通过共价键连接, 3个SH基团与Co原子通过配位键相连, 从而形成化合物3。化合物2和3分别用红外、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: 钴 碳硼烷 配体 偶联 | |
| 基金项目: 国家自然科学基金(No.21361022, 21261020)、第54批中国博士后科学基金面上基金(No.2013M541640)、南京大学配位化学国家重点实验 室第25批开放课题资助项目。 | |
| Abstract: Half-sandwich 16e complex CpCoS2C2B10H10 (Cp: cyclopentadienyl) (1) reacted with HC≡CCO2Me in the presence of 2-methylpropanedithioic acid to generate compounds {(C5H4CoS2C2B9H9)(CH=CHCO2Me)(Me2C=CS2H)} (2) and (Me2C=CS2H)3Co (3). In 2, one S-Co bond of 1 was broken, and the S atom linked with the terminal acetylenyl carbon atom of the HC≡CCO2Me. Meanwhile, the Co atom in 1 linked to the S atom in 2-methylpropanedithioic acid with covalent bond while linked to the SH unit with coordinative bond. One carbon atom of Cp ring linked to the B(3)/B(6) cite of the carborane cage. The H atom of the B(3)/B(6) cite migrated to the internal acetylenyl carbon atom to form a trans-ethylenic bond. The Co atom of 1 linked to three S atoms of three 2-methylpropanedithioic acid molecules with covalent bond, while linked to the other three SH units with coordinative bond. As a result, product 3 formed. Complexes 2 and 3 have been characterized by IR, NMR, elemental analysis, mass spectrum and single-crystal X-ray diffraction analysis. | |
| Keywords: cobalt carborane ligand couple | |
| 投稿时间：2015-03-29 修订日期：2015-05-08 | |
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| 叶红德,徐宝华,胡久荣,燕红.钴(Ⅲ)催化CpCoS2C2B10H10分子内B(3)/B(6)位和Cp配体偶联[J].无机化学学报,2015,31(7):1447-1452. | |
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