Formation of Oxalate- and Formate-Containing Lanthanide Complexes via the Activation of Carbon Dioxide

• Main Authors: Yen-Pai Chi, 紀彥百
• Other Authors: 曾添文
• Format: Others
• Language: zh-TW
• Published: 2009
• Online Access: http://ndltd.ncl.edu.tw/handle/v9peq3

碩士 === 國立臺北科技大學 === 化學工程研究所 === 97 === (1) CO2 activation toward the formation of oxalate and formate in lanthanide compounds Treatment of MNO3•nH2O (M = Er, Eu, Tb) with 2,4,6-tri(2-pyridyl)-1,3,5-triazine in acetonitrile under solvothermal conditions led to the formation 1-D coordination polymers of Er2(C18H12N6)2(NO3)4(HCOO)(CH3COO) (1), Eu2(C18H12N6)2(NO3)4(HCOO)(CH3COO) (2), Tb2(C18H12N6)2(NO3)4(HCOO)(CH3COO) (3). Single-crystal X-ray diffraction analysis revealed that the lanthanide metal centers are bridged by one formate and one acetate ligand. Under similar conditions, the coordination polymer of Er2(C18H12N6)2(NO3)4(C18H12N6)(H2O) (1a) with an oxalate-bridging group was obtained. The discussion focuses carbon dioxide activation toward the formation of oxalate or formate under different condition. Treatment of Er(NO3)3•5H2O and HCOONa with 4''-(4-methylphenyl)-2,2'':6'',2''-ter-pyridine in acetonitrile under solvothermal conditions led to the formation of complex Er2(C22H17N3)2(NO3)4(HCOO)2 (4). This complex is a dimetallic specie with a disorder formate-bridging group. The disorder of formate and oxalate moieties in the crystal structure of Sm2(C22H17N3)2(NO3)4 (C2O4)0.5(HCOO) (4a) was discussed. (2) Synthesis of coordination polymers Treatment of Er(NO3)3•5H2O, MnCl2•4H2O or CoCl2•6H2O with 4''-(p-carboxylphenyl)-2,2'':6'',2''-terpyridine in aqueous solution under hydrothermal conditions led to the formation of coordination polymers of [Er2(C22H14N3O2)6 ]n (5), [Mn(C22H14N3O2)2•H2O]n (6) or Co(C22H14N3O2)2 •4H2O (7), respectively. Compounds 1-7 were characterized using elemental analysis, IR, thermal analysis and X-ray powder diffraction studies. The structures of these compounds were further confirmed by single-crystal X-ray diffraction analysis.