论文部分内容阅读
半夹芯16e化合物Cp Co S2C2B10H10(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{(C5H4Co S2C2B9H9)(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。
The semi-sandwich 16e compound Cp Co S2C2B10H10 (Cp: cyclopentadienyl) (1) is reacted with HC≡CCO2Me in the presence of 2-methyldithiopropionic acid to give the compound {(C5H4Co S2C2B9H9) (CH═CHCO2Me) (Me2C = CS2H) } (2) and (Me2C = CS2H) 3Co (3). In compound 2, one S-Co bond in the starting compound 1 is cleaved, and this S atom is attached to a terminal alkyne carbon atom of HC≡CCO2Me. Co atom and 2-methyl dithiopropionic acid S atom bonding, 2-methyl dithiopropionic acid molecule SH group and the Co atom through the coordination bond is connected; the same time, Cp ring a carbon The atom is linked to the B (3) / B (6) position of the carborane cage and the hydrogen atom at the B (3) / B (6) site migrates to the internal alkynyl carbon atom of the alkyne HC≡CCO2Me to form an anti The olefinic bond. The three S atoms in the three 2-methyldithiopropionic acid molecules are respectively covalently linked to the Co atoms in 1, and the 3 SH groups are connected to the Co atoms through coordination bonds to form compound 3. Compounds 2 and 3 were characterized by IR, NMR, elemental analysis, mass spectrometry and single crystal X-ray diffraction analysis.