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陆森红盐

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陆森红盐
IUPAC名
potassium tetranitrosyl-di-μ-sulfidodiiron(Fe–Fe)(2–)
别名 二(μ-硫基)四亚硝基合二铁酸钾
识别
CAS号 58204-17-4  ☒N
性质
化学式 Fe2N4K2O4S2
摩尔质量 374.04 g·mol⁻¹
外观 暗红色晶体
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

陆森红盐(英語:Roussin's Red Salt)是一种分子式为K2[Fe2S2(NO)4]的无机化合物。这种亚硝酰配合物于1858年由法国化学家M.L. Roussin首次描述报道,它和陆森黑盐是第一批人工合成的铁硫簇合物,也是第一批过渡金属簇合物。[1]

结构和化学键

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陆森红盐的阴离子是由一对Fe(NO)2通过两个硫原子作为边桥基配位构成的双四面体,亚硝基配体作为一个三电子给体使得Fe-NO键是线性结构的。[2]陆森红盐作为抗磁性化合物符合十八电子规则,两个铁原子的氧化态均为-1价。

合成方法

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最初Roussin报道的合成方法是从硝普钠的阴离子[Fe(CN)5NO]2−和硫单质反应得到的。[3]也可由硫化物与铁的亚硝酰卤化物反应制备:[4]

Fe2I2(NO)4 + 2Li2S → Li2Fe2S2(NO)4 + 2LiI

陆森红盐的酯可通过对陆森红盐进行烷基化反应制得:

Li2Fe2S2(NO)4 + 2 RX → Fe2(SR)2(NO)4 + 2 LiX

陆森红盐的酯也可由Fe2I2(NO)4硫醇反应制得。

参考资料

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  1. ^ Roussin, M. L. Recherches sur les nitrosulfures doubles de fer (nouvelle classe de sels). Ann. Chim. Phys. 1858, 52: 285–303 [2012-09-26]. (原始内容存档于2015-11-06) (法语). 
  2. ^ J. T. Thomas, J. H. Robertson and E. G. Cox. The crystal structure of Roussin's red ethyl ester. Acta Crystallographica. 1958, 11: 599–604. doi:10.1107/S0365110X58001602 (英语). 
  3. ^ Hans Reihlen, Adolf v. Friedolsheim. Über komplexe Stickoxydverbindungen und das sogenannte einwertige Eisen. Justus Liebig's Annalen der Chemie. 1927, 457: 71–82 [2012-09-26]. doi:10.1002/jlac.19274570103. (原始内容存档于2015-11-06) (德语). 
  4. ^ TB Rauchfuss, TD Weatherill. Roussin's Red Salt revisited: reactivity of Fe2(μ-E)2(NO)42-(E= S, Se, Te) and related. Inorganic Chemistry. 1982, 21 (2): 827–830 [2012-09-26]. doi:10.1021/ic00132a071. (原始内容存档于2019-07-13) (英语). 

参见

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陆森红盐
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