含多芽氮配位基與硝酸金屬化合物的合成與結構研究

Synthesis and Structures of Metal(II)Nitrate Complexes Containing Polydentate Nitrogen Ligands

林文彬(Wen-Ben Lin)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2001年)

https://doi.org/10.6840/cycu200100276

摘要

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。

關鍵字

硝酸金屬 ； 多芽氮配位基

並列摘要

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.

並列關鍵字

Polydentate Nitrogen Ligands ； Metal(II) Nitrate Complexes

參考文獻

(2) Hurley, T. J, ;Robinson, M.A. Inorg. Chem., 1968, 7, 33.

(3) Rodig, O. R.; Brueckner, T.; Hurlburt, B. K.; Schlatzer, R. K.; Venable T. L.; Sinn, E. J. Chem. Soc. Dalton Trans. 1981, 196.

(10) Cotton, F. A.; Daniels, L. M.; T.; Murillo, C. A.; Wang, X. Chem.Commun. 1998, 39.

(11) Cotton, F. A.; Daniels, L. M.; T.; Murillo, C. A.; Wang, X. Inorg. Chem.Commun. 1998, 1, 281.

(14) P.-Y Yang, F.-C. Chang, M.-C. Suen, J.-D. Chen, T.-C. Keng, J.-C. Wang, J. Organoment. Chem., 2000, 596, 281.