Synthesis and Characterization of New Iron Complexes Induced with y-Ray Irradiation

y 射线辐照诱导新型铁配合物的合成和表征

• 批准号: 16550059
• 负责人: MOTOMI Katada
• 金额: $ 2.05万
• 依托单位: Tokyo Metropolitan University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550059/
• 关键词: induced irradiation; radiolysis; Mossbaue spectra; γ-ray; iron complexes; iron(III) oxalates; iron(III) citrate; iron(II) oxalates; シュウ酸鉄(II)錯体; メスバウアー分光法; 放射線分解生成物; ガンマ線照射; マロン酸鉄錯体

Materials. Fe2(C2O4)3・6H2O, [LaFe(C2O4)3]・9H2O, [bipyH][Fe(C2O4)2(H2O)2]・H2O,[phenH][Fe(C2O4)2(H2O)2] H2O, (Hpy)2[Fe2(C6H4O7)2(H2O)2], (Hbpiy)2[Fe2(C6H4O7)2(H2O)2] and (Hphen)3[Fe2(C6H4O7)3] complexes were prepared and irradiated with 60Co γ-ray. New iron(II) species were observed in these complexes. New iron(II) high-spin species of irradiated Fe2(C2O4)3.6H2O and [LaFe(C2O4)3]・9H2O were assigned to FeC2O4・2H2O by using Mossbauer spectroscopy and XRD. However, new iron(II) high-spin species of [bipyH][Fe(C2O4)2(H2O)2] H2O, [phenH][Fe(C2O4)2(H2O)2] ・H2O and iron citrate were different with FeC2O4・2H2O. It is well known in radiation chemistry that the reduction of iron atoms in trisoxalatoferrate(III) is associated with following radiolysis of oxalate anions, C2O42-→2CO2 + 2e-. In this system, formation fo Fe(II) species is explaine by the same reason.In [bipyH][Fe(C204)2(H20)・H2O, [phenH][Fe(C2O4)2(H2O)・H2O, (Hbpiy)2[Fe2(C6H4O7)2(H2O)2] and ( Hphen)3[Fe2(C6H4O7)3] complexes, another new Fe(II) low-spin species were found with increase of irradiation dose. Its new species was assigned to Fe(bipy)33+ and Fe(phen)33+ by Mossbauer spectra. This result is explained by the reaction fo Fe2+ ion and bipyridine and phenanthroline ligands which resist radiation. Malonate iron complexe K3[Fe(C2H2O4)3]・3H2O were also observed Fe(II) high-spin species by y-ray irradiation.In mixture of K3Fe(C2O4)3 and Co(bipy)3・Cl2 and Co(phen)3・Cl2, Fe(II) high-spin species was observed due to K3Fe(C2O4)3 itself but new Fe(II) low-spin species was not found. It suggests that the chemical bond strength of Co-bipy and Co-phen greater than those of Fe-bipy and Fe-phen. New iron species were not found in irradiated (Hphen)3[Fe(CN)6]・5H2O and (Hphen)3[Fe(CN)5NO]・2H2O. It suggest that the radiation resisting of CN ligand is stronger than those of oxalate, citrate and malonate ligands.We obtained new iron species by y-ray irradiation of iron complexes containing oxalate, citrate, malonate.

材料。合成了Fe2(C2O4)3·6H2O、[LaFe(C2O4)3]·9H2O、[bipyH][Fe(C2O4)2(H2O)2]·H2O、[PhenH][Fe(C2O4)2(H2O)2]H2O、(Hpy)2[Fe2(C6H4O7)2(H2O)2]、(Hbpiy)2[Fe2(C6H4O7)2(H2O)2]、(Hbpiy)2[Fe2(C6H4O7)2(H2O)2]和(Hphen)3[Fe2(C6H4O7)3]。在这些络合物中观察到了新的铁(II)物种。用穆斯堡尔谱和X射线衍射法确定了辐照后的Fe2(C2O4)3.6H2O和[LaFe(C2O4)3]·9H2O中新的Fe(II)高自旋物种为FeC2O4·2H2O。然而，新的铁(II)高自旋物种[bipyH][Fe(C2O4)2(H2O)2]H2O、[PhenH][Fe(C2O4)2(H2O)2]·H2O和柠檬酸铁与FeC2O4·2H2O不同。在辐射化学中众所周知，三草酸高铁酸盐(III)中铁原子的还原与草酸根阴离子C2O42-→2CO2+2E-的辐射分解有关。在[bipyH][Fe(C204)2(H20)·H2O，[PhenH][Fe(C2O4)2(H2O)·H2O，(Hbpiy)2[Fe2(C6H4O7)2(H2O)2]和(Hphen)3[Fe2(C6H4O7)3]中，随着辐照剂量的增加，还发现了新的Fe(II)低自旋物种。经穆斯堡尔谱鉴定其新物种为Fe(Bipy)33+和Fe(Phen)33+。这一结果可以通过Fe2+离子与联吡啶和邻菲罗啉配体的反应来解释。在K3Fe(C2O4)3和Co(Bipy)3·Cl2和Co(Phen)3·Cl2的混合物中，由于K3Fe(C2O4)3本身的原因，观察到了Fe(II)的高自旋物种，但没有发现新的Fe(II)低自旋物种。结果表明，Co-bipy和Co-phen的化学键强度大于Fe-bipy和Fe-phen。辐照后的(Hphen)3[Fe(CN)6]·5H2O和(Hphen)3[Fe(CN)5NO]·2H2O中未发现新的铁物种。结果表明，CN配体比草酸、柠檬酸和丙二酸具有更强的抗辐射能力。我们用γ-射线辐照草酸、柠檬酸、丙二酸的铁络合物得到了新的铁物种。