配合物[Ni(IDB)_2][C_6H_4(OH)COO]·ClO_4·CH_3CH_2OH·H_2O催化尿素水解的机理及其电化学性质

报道Ni(H2O)6](ClO4)2·2H2O的合成、晶体结构,单核镍(Ⅱ)配合物Ni(IDB)2]C6H4(OH)COO]·ClO4·CH3CH2OH·H2O配体IDB为N,N 二(2 苯并咪唑亚甲基)胺]的电化学性质,探讨标题配合物催化尿素水解的机理。X射线单晶衍射表明,Ni(H2O)6](ClO4)2·2H2O晶体属单斜晶系,P2(1)/C空间群,化学式:Cl2H16O16Ni,Mr=401.74,晶胞参数:a=0.62383(12)nm,b=1.2464(3)nm,c=0.91845(18)nm,α=90°,β=106.93(3)°,γ=90°,V=0.6832(2)nm3,Z=2,F(000)=412,S=1.079,DC=1.953g/cm3,μ=1.890mm-1。最终因子RI>2σ(I)]:R1=0.0423,wR2=0.1155;R(全部数据)∶R1=0.0506,wR2=0.1180。结构分析表明,Ni(H2O)6](ClO4)2·2H2O的镍(Ⅱ)分别与6个H2O配位形成对称的正八面体构型。循环伏安实验说明,标题配合物在DMF溶液中在E1/2=0.884V处经历了一个准可逆的一电子氧化还原过程。

Catalytic mechanism of complex [Ni(IDB)2][C6H4(OH)COO]·ClO4·CH3CH2OH·H2O in the hydrolysis of urea and its electrochemical property

The synthesis and the crystal structure of Ni(H_2O)_6](ClO_4)_2·2H_2O and the electrochemical property of mononuclear nickel(Ⅱ) complex C_6H_4(OH)COO]·ClO_4·CH_3CH_2OH·H_2O IDB=N,N-bis(benzimidazol-2-ylmethyl) amine] reported. The catalytic mechanism of the title complex in the hydrolysis of urea is discussed. The crystal structure of Ni(H_2O)_6](ClO_4)_2·2H_2O has been determined by single crystal X-ray diffraction. The crystal belongs to monoclinic system,space group P2(1)/C, chemical formula: Cl_2H_(16)O_(16)Ni, M_r=401.74, with the crystal cell parameters: a=0.62383(12) nm,b=1.2464(3) nm, c=0.91845(18) nm, α=90°,β=106.93(3)°, γ=90°, V=0.6832(2) nm~3, Z=2, F(000)=412,S=1.079,D_C=1.953 g/cm~3, μ=1.890 mm~(-1).The final R:R_1=0.0423,wR_2=0.1155;R(all data):R_1=0.0506,wR_2=0.1180. The nickel(Ⅱ) atom in Ni(H_2O)_6](ClO_4)_2·2H_2O has symmetrical octahedron coordination geometry and is six coordinated by six oxygen atoms from H_2O. Cyclic voltammetry experiment shows that the title complex in DMF under goes a quasi reversible one electron redox reaction at E_(1/2)=0.884 V.