本論文主要探討含多芽氮配位基和硝酸金屬化合物鍵結的化學 以化合物Ni(NO3)2 6H2O為起始物和配位基Hdpa ( Hdpa = 2,2'-dipyridylamine)在MeOH下反應,可得化合物[Ni(Hdpa)2(NO3)](NO3), 1。而以Cd(NO3)2 4H2O為起始物和配位基HDpyF (HDpyF = Bis(2-pyridyl)formamidine)在MeOH下反應,可得化合物[Cd2(DpyF)3]2[Cd(NO3)4], 2。其中,DpyF-以一全新的鍵結模式配位至雙鎘中心原子,而四個硝酸根皆以雙配位模式配位至中心Cd金屬,形成罕見八配位Cd化合物。以M(NO3)2 6H2O (M = Ni, Co)為起始物與二當量的HDpyF在CH3CN中反應,可得M(HDpyF)2(NO3)2 (M = Ni, 3; M = Co, 4),將其溶於CH2Cl2,以ether擴散養晶。於長時間後得M(C6H6N2O)2(NO3)2 (M = Ni or Co)晶體。由M(NO3)2 6H2O (M = Ni, Co)為起始物與二當量的HDMpyF (HDMpyF = Bis(2-(6-methylpyridyl)formamidine)在CH3CN中反應,及以Cd(NO3)2 4H2O為起始物與二當量的HDMpyF在MeOH中反應可得化合物M(HDMpyF)2(NO3)2 (M = Ni, 5; M = Co, 6; M = Cd, 7)。化合物5、6、7中HDMpyF配位基皆以雙配位形式配位於金屬中心。以二當量Cd(NO3)2 4H2O與三當量HDMpyF在MeOH中反應可得化合物[Cd2(DMpyF)3](NO3), 8,其中DMpyF-配位基以四配位形式配位於金屬Cd中心。化合物1~8之結構皆以單晶X-ray繞射儀解析決定。
This thesis discusses the chemistry of Metal(II) nitrate complexes containing polydentate nitrogen ligands. The reaction of Ni(NO3)2 6H2O with Hdpa ( Hdpa = 2,2'-dipyridylamine) in MeOH afforded the complex [Ni(Hdpa)2(NO3)](NO3), 1. The reaction of Cd(NO3)2 4H2O with HDpyF (HDpyF = Bis(2-pyridyl)formamidine) in MeOH afforded the complex [Cd2(DpyF)3]2[Cd(NO3)4], 2. Each DpyF- ligand of Cd2(DpyF)3+coordinates to central dicadmium in a new bonding mode. The cadmium ion in Cd(NO3)42- exhibits the rare coordination number of 8. Complexes M(HDpyF)2(NO3)2 (M = Ni, 3; M = Co, 4) were prepared by reaction of M(NO3)2 6H2O (M = Ni, Co) with HDpyF in CH3CN. Crystals of M(C6H6N2O)2(NO3)2 (M = Ni or Co) were obtained by dissolving M(HDpyF)2(NO3)2 in CH2Cl2 and then layered with ether for a period of time. Complexes M(HDMpyF)2(NO3)2 (M = Ni, 5; M = Co, 6 M = Cd, 7) were prepared by reacting of M(NO3)2 6H2O with HDMpyF in appropriate solvents. The HDMpyF ligands in complexes 5, 6 and 7 were coordinated to the metal centers in bidentate bonding mode. The reaction of two equivalents of Cd(NO3)2 4H2O with three equivalents of HDMpyF in MeOH afforded the complex [Cd2(DMpyF)3](NO3), 8. The HDMpyF ligand in complex 8 coordinates to the metal center in a tetradentate bonding mode. Complexes 1~8 were determined by X-ray crystallography.