- 學位論文
二氧化碳活化生成含草酸與甲酸之鑭系金屬錯合物
Formation of Oxalate- and Formate-Containing Lanthanide Complexes via the Activation of Carbon Dioxide
摘要
本論文分兩部分 (一) 二氧化碳活化生成含草酸與甲酸之鑭系化合物 本研究是將二氧化碳活化轉換成草酸和甲酸形式之研究。利用 2,4,6-tri(2-pyridyl)-1,3,5-triazine 與金屬離子鉺、銪、鋱進行水熱法自組裝合成，得到配位化合物 [M2(C18H12N6)2(NO3)4(HCOO)(CH3COO) ]n (M = Er、Eu、Tb) (1) ~ (3)，上述之化合物皆以 formate 和 acetate 當作橋鍵。發現此反應在相近的條件下可以得 到以 oxalate 為橋鍵的配位化合物 Er2(C18H12N6)2(NO3)4(C2O4)(H2O) (1a)。探討在何種條件下可將二氧化碳活化轉換成草酸或是甲酸形式，是本論文的重點。 利用4'-(4-methylphenyl)-2,2':6',2'-terpyridine 與鉺金屬離子和甲酸鈉進行水熱法自組裝合成，得到配位化合物 Er2(C22H17N3)2(NO3)4(HCOO)2 (4)，以 formate 當作橋鍵。並對化合物 Sm2(C22H17N3)2(NO3)4 (C2O4)0.5(HCOO) (4a) 的結構中，草酸與甲酸兩橋鍵配子的 disorder 問題作了詳細解析。 (二) 含pyridine與carboxylic acid之配子自組裝合成配位聚合物 利用4'-(p-carboxyphenyl)-2,2':6',2'-terpyridine 與鉺、錳和鈷等金屬離子進行水熱法自組裝合成。硝酸鉺為反應物時得到配位化合物 [Er2(C22H14N3O2)6 ]n (5)，取氯化錳反應得到配位化合物 [Mn(C22H14N3O2)2•H2O]n (6)，而取氯化鈷反應則得到配位化合物 Co(C22H14N3O2)2 •4H2O (7)。探討配位聚合物之結構與性質分析。
並列摘要
(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.