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

材料，以及Fe2（C2O4）3·6 H2O， [LaFe（C2O4）3]·9 H2O， [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 60 Co γ-ray。新铁（II）物种在这些复合体中被观察到。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？（II） high-spin species of [bipyH][Fe（C2O4）2（H2O）2] H2O， [phenH][Fe（C2O4）2（H2O）2] ·H2O and？citrate were different with FeC2O4·2 H2O。众所周知的辐射化学，即三氮甲酸酯（III）中铁原子的减少与氧化物的后续放射性有关，C2 O 42-→ 2CO 2 + 2 e-。在这个系统中，形成Fe（II）物种的原因是相同的。在[bipyH][Fe（C204）2（H20）·H2O， [phenH][Fe（C2 O 4）2（H2O）·H2O， （Hbpiy）2[Fe 2（C6 H4 O 7）2（H2O）2]和（ Hphen）3[Fe 2（C6 H4 O 7）3]复合体，另一种新的Fe（II）低自旋物种发现了含有含辐照剂量的突变。Mossbauer Spectra的新品种被指定为Fe（bipy）33+和Fe（phen）33+本结果是由Fe 2+离子和双吡啶和苯丙氨酸配体的抗辐射作用解释的。Malonate iron complexe K3[Fe（C2 H2O 4）3]·3 H2O也是可见的Fe（II）高自旋特性由Y射线红外辐射引起的。在K3 Fe（C2 O 4）3 and Co（bipy）3·Cl 2 and Co（phen）3·Cl 2，Fe（II）高自旋物种已被观测到K3 Fe（C2 O 4）3本身，但尚未发现新的Fe（II）低自旋物种。它建议其化学结合强度的钴和钴比Fe-bipy和Fe-phen更重要。New iron species were not found in irradiated （Hphen）3[Fe（CN）6]·5 H2O and （Hphen）3[Fe（CN）5 NO]·2 H2O。它建议CN配体的辐射抵抗力大于氧化物、柠檬酸和malonate配体的那些，我们通过y射线irradiation的铁复合体发现了含有氧化物、柠檬酸和malonate的新铁物种。

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.