使用氯化亞鐵和經由三氟醋酸酸化過的[H4HAPP(TFA)2]進行反應，經過清洗後，再利用甲醛與產物進行加熱迴流，使其溶解度增加，再利用過量HCl 合成出[Fe(H2HAPP)Cl2]Cl，由電灑質譜發現在 含水溶劑中，有雙核錯合物的產生，在利用元素分析、電子吸收光 譜、氫核磁共振光譜，可以判定[Fe(H2HAPP)Cl2]Cl 單核錯合物在含水溶液中確實可以自氧化形成μ-oxo dimer 雙核鐵錯合物，而由於μ-oxo dimer 雙核鐵錯合物在水溶液中還具有氧化的現象，由電子吸收光譜從655nm 吸收峰紅位移至830 nm 吸收峰，以及氫核磁共振光譜所表示的積分值剛好為1:2，此現象讓我們由原本推測μ-oxo dimer 雙核鐵錯合物氧化態的改變所造成紅位移現象，而開始大膽假設μ-oxo dimer 雙核鐵錯合物，在水溶液中也可以自身氧化形成三核錯合物的可能，由其在加熱及添加氧化劑的電子吸收光譜，皆可以促進三核錯合物加速升成，也利用透光薄層電極( OTTLE )，來加以氧化水溶液中的錯合物，也可以發現同樣的結果。 有了此推測，我們也對水溶液中進行錯合物的性質研究，由於H2HAPP 橋基氮上可以接受或提供質子，因此對電子吸收光譜酸鹼 滴定可得到pKa=4.07，也利用pyridine 及imidazole 來進行軸向配位置換，也經由電灑質譜及電子吸收光譜證實之。 In this research, [Fe(H2HAPP)Cl2]Cl had been synthesized by acidified the ligand [H4HAPP(TFA)2] by TFA and reacted with FeCl2. The product were refluxed with formaldehyde to increase the solubility and recrystalized by add excess HCl. [Fe(H2HAPP)Cl2]Cl were characterized by EA, ESI-MS, NMR. The ESI-MS result revealed that the complex were able to form the dimmer form in water-contained solvent. The coupling processes were proofed by temperature-varition NMR and absorption spectra. The NMR spectrum of [Fe(H2HAPP)Cl2]Cl in D2O showed broad peaks at 3.99 ppm(b)、6.55 ppm(b)、10.87 ppm(b) and sharp peaks at 7.10 ppm (d) 、 7.15 ppm (d)、7.82 ppm (s)、7.89 ppm (s)、8.46 ppm (d)、8.58 ppm (d) implied the trimer form of complexes. This hypothesis were researched by redox absorption spectra and OTTLE spectroscopy technique. The property of the complex in water has researched. The absorption spectrum of acid / base titrate the trimer complex shows pKa=4.07, due to the bridged N of H2HAPP can be proton receptor and donor. Utilize pyridine and imidazole to possess axial replacement, which also can be confirmed by ESI-MS and absorption spectrum.
