A new compound[CpCo(Se_2C_2B_(10)H_9)CH_2C(O)C_4H_3O]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 P2_1/c with a=10.9481(10),b=24.6600(12),c=25.7430(14)A,β=100.863(3)°,C_(42)H_(57)B_(30)Co_3O_6Se_6·CH_2Cl_2·0.25H_2O,M_r=1722.16,V=6825.6(8)A^3,D_c=1.676 g/cm^3,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(Se_2C_2B_(10)H_(10))and alkyne 1-(2-furyl)-2-propyn-1-one.The hydrogen atom in the B(3)position of CpCo(Se_2C_2B_(10)H_(10))has been activated and migrated to the terminal carbon of 1-(2-furyl)-2-propyn-1-one to form the B-CH_2 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。
