A structural study of the hydrated and the dimethylsulfoxide, N,N′-dimethylpropyleneurea, and N,N-dimethylthioformaraide solvated iron(II) and iron(III) ions in solution and solid state
A structural study of the hydrated and the dimethylsulfoxide, N,N′-dimethylpropyleneurea, and N,N-dimethylthioformaraide solvated iron(II) and iron(III) ions in solution and solid state
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DOI：
10.1016/j.ica.2006.09.014
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发表时间：
2007-04-20
影响因子：
2.8
通讯作者：
Persson, Ingmar
中科院分区：
文献类型：
--
作者：
Lundberg, Daniel;Ullstrom, Ann-Sofi;Persson, Ingmar
用扩展X射线吸收精细结构(EXAFS)研究了Fe(II)和Fe(III)离子在水、二甲基亚砜(Me2SO)、N，N‘-二甲基丙基脲(DMPU)和硫磺给电子剂N，N-二甲基硫代甲酰胺(DMTF)三种给氧溶剂中的结构，这些溶剂具有不同的配位和溶剂化性质。此外，还测定了六(二甲基亚砜)高氯酸铁(III)的结晶学结构，以支持溶液中相应溶剂的测定。水合、二甲基亚砜和N，N-二甲基硫代甲酰胺溶剂化Fe(II)离子在溶液和固体中均呈规则的八面体配位，平均Fe-O，Fe-O和Fe-S键距分别为2.10，2.10和2.52埃，而N，N‘-二甲基丙基脲铁(II)溶剂为五配位，d(Fe-O)=2.06埃。这些化合物的颜色从浅绿色(水合物)到深橙色或红色(DMPU)不等。水合Fe(III)离子与二甲基亚砜溶剂化Fe(III)离子在溶液和固体中均呈预期的八面体配位，Fe-O键距均为2.00埃，而N，N‘-二甲基丙基尿素铁(III)的溶剂为五配位，平均Fe-O键距为1.99埃。N，N-二甲基硫代甲酰胺在固体高氯酸盐中的溶剂化Fe(III)离子是四配位的，Fe-S平均键距为2.20埃。在N，N-二甲基硫代甲酰胺溶液中，铁(III)随时间还原为铁(II)。这些化合物的颜色从淡黄色(水合物)到黑红色(DMPU)不等。(C)2006爱思唯尔B.V.保留所有权利。
The structures of the solvated iron(II) and iron(III) ions have been studied in solution and solid state by extended X-ray absorption fine structure (EXAFS) in three oxygen donor solvents, water, dimethylsulfoxide (Me2SO), N,N'-dimethylpropyleneurea (DMPU), and one sulfur donor solvent, N,N-dimethylthioformamide (DMTF); these solvents have different coordination and solvation properties. In addition, the structure of hexakis(dimethylsulfoxide)iron(III) perchlorate has been determined crystallographically to support the determination of the corresponding solvate in solution. The hydrated, the dimethylsulfoxide and N,N-dimethylthioformamide solvated iron(II) ions show regular octahedral coordination in both solution and solid state with mean Fe-O, Fe-O, and Fe-S bond distances of 2.10, 2.10, and 2.52 angstrom, respectively, whereas the N,N'-dimethylpropyleneurea iron(II) solvate is five-coordinated, d(Fe-O) = 2.06 angstrom. The compounds vary in color from light green (hydrate) to dark orange or red (DMPU). The hydrated iron(III) ion in aqueous solution and the dimethylsulfoxide solvated iron(III) ions in solution and solid state show the expected octahedral coordination, the Fe-O bond distances are 2.00 angstrom for both, whereas the N,N'-dimethylpropyleneurea iron(III) solvate is found to be five-coordinated with a mean Fe-O bond distance of 1.99 angstrom. The N,N-dimethylthioformamide solvated iron(III) ion in the solid perchlorate salt is tetrahedrally four-coordinated, the mean Fe-S bond distance is 2.20 angstrom. Iron(III) is reduced with time to iron(II) in N,N-dimethylthioformamide solution. The compounds vary in color from pale yellow (hydrate) to blackish red (DMPU). (C) 2006 Elsevier B.V. All rights reserved.