化学学报 ›› 1987, Vol. 45 ›› Issue (1): 33-39. 上一篇    下一篇

研究论文

气相色谱法研究配位化合物的热稳定性XVIII: 配位CN离子的活化加氢

牛均宁;忻新泉;戴安邦   

  1. 南京大学配位化学研究所
  • 发布日期:1987-01-15

Studies on thermal stabilities of coordination XVIII.Activation and hydrogenation of coordinated CN ion

NIU JUNNING;XIN XINQUAN;DAI ANBANG   

  • Published:1987-01-15

根据一系列金属(Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag、Sn、La)的六氰合铁(II)、(III)酸盐在H2气分中热分解时所发生的CN^-加氢反应,从晶体结构和电子结构两方面探讨了双金属双端配位对CN^-的活化作用和CN^-的加氢反应机理.研究了CN^-的活化程度与配位金属离子的还原电位及d电子组态之间的关系.

关键词: 反应机理, 气相色谱, 晶体结构, 氢化, 热稳定性, 铁蓝, 电子结构, 氰络合物, 双金属催化剂, 络合物化学

M3[Fe(CN(2]2 (M = Mn, Co, Ni, Cu, Zn), Sn9Fe(CN(6], KFe[Fe(CN)6],K2Co[Fe(CN)6)], M1[Fe(CN)6] (M1 = Cr, Fe), Ag3[Fe(CN)6], and La[Fe(CN)6] may be considered as a multibond activation model of bimetal coordination, since CN- acts as a typical ambident ligand bonded at the 2 ends with 2 metal ions. In accordance with hydrogenation reactions of CN- taking place during thermal decomposition in H, the activation effect of bimetal coordination and the mechanism of hydrogenation reaction of CN- are discussed from the viewpoint of the crystal structure and of the electronic structure of the complexes. The activation degree of CN- bonded with various metal ions was studied. The temperature at which the triple bond of CN- breaks with top speed to evolve NH3 correlates closely with the standard electrode potential and d electron configuration of the metal ions.

Key words: REACTION MECHANISM, GAS CHROMATOGRAPHY, CRYSTAL STRUCTURE, HYDROGENATION, THERMAL STABILITY, IRON BLUE, ELECTRONIC STRUCTURE, CYANO COMPLEX, DUAL METAL REFORMING CATALYST, COORDINATE CHEMISTRY

中图分类号: