A new compound [CpCo(Se2C2BIoH9)CH2C(O)C4H30] has been synthesized and characterized by elemental analysis, IR spectroscopy, NMR, MS and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group P21/c with a = 10.9481(10), b = 24.6600(12), c = 25.7430(14) A, β = 100.863(3)°, C42H57B30Co306Se6"CH2C12"0.25H20, Mr = 1722.16, V = 6825.6(8) A3, Dc= 1.676 g/cm3, Z = 1 and F(000) = 3346. The molecular structure shows a 1:1 ratio product of the two reactants of 16e half-sandwich complex CpCo(Se2C2B10H10) and alkyne 1-(2-furyl)-2-propyn-l-one. The hydrogen atom in the B(3) position of CpCo(Se2C2B10HIo) has been activated and migrated to the terminal carbon of 1-(2-furyl)- 2-propyn-l-one to form the B-CH2 unit. The title compound molecules are linked and extended further into a one-dimensional chain through atypical hydrogen bonds.
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。