七氟化铼

七氟化铼
IUPAC名
rhenium heptafluoride, heptafluoridorhenium
识别
CAS号 17029-21-9  checkY
PubChem 123369
ChemSpider 26323924
SMILES
 
  • F[Re](F)(F)(F)(F)(F)F
InChI
 
  • 1/7FH.Re/h7*1H;/q;;;;;;;+7/p-7/rF7Re/c1-8(2,3,4,5,6)7
InChIKey HFHBKXWKPQUYIA-KLJGHBABAK
性质
化学式 ReF7
摩尔质量 319.196 g·mol⁻¹
外观 亮黄色固体
密度 4.3g/cm3
熔点 48.3°C
沸点 73.72°C
溶解性 水解
蒸氣壓 13.41 kPa[1]
结构
晶体结构 三斜晶系aP16
空间群 P-1, No. 2
热力学
ΔfHfus 7.53 kJ/mol[1]
ΔfHvap 30.77 kJ/mol[1]
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

七氟化铼的最高价氟化物,化学式为ReF7。它是一种黄色低熔点的固体[2],是唯一在热力学上稳定的金属七氟化物,[3]也是含氟计量比(M:F=1:7)最高的过渡金属氟化物,它的7个价电子全部用于与氟成键。[4]1.5 K温度下的中子衍射实验证实它采用了变形的五角双锥结构,与七氟化碘类似。[5]电子衍射实验证实这个结构是非刚性的。 [6]

制备及性质

它可由金属气在400°C直接化合制得:[7]

2Re + 7 F2 → 2 ReF7

七氟化铼在碱性条件下水解,生成高铼酸氢氟酸[1]

ReF7 + 4H2O → HReO4 + 7HF

它与氟离子的供体作用(如氟化铯)可以生成ReF8阴离子,后者具有四方反棱柱的空间构型。[8]与强路易斯酸(氟离子受体,如五氟化锑)作用可以生成ReF6+阳离子。[7]

参考文献

  1. ^ 1.0 1.1 1.2 1.3 J.G.Malm; H.Selig. The vapour-pressures and other properties of ReF6 and ReF7. Journal of Inorganic and Nuclear Chemistry. 1961, 20 (3): 189–197. doi:10.1016/0022-1902(61)80267-4 (英语). 
  2. ^ Rouschias, George. Recent advances in the chemistry of rhenium. Chemical Reviews. 1974-10-01, 74 (5): 531–566. doi:10.1021/cr60291a002. 
  3. ^ Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4. 
  4. ^ Jianyan Lin, Ziyuan Zhao, Chunyu Liu, Jing Zhang, Xin Du, Guochun Yang, Yanming Ma. IrF 8 Molecular Crystal under High Pressure. Journal of the American Chemical Society. 2019-04-03, 141 (13): 5409–5414 [2021-11-16]. ISSN 0002-7863. doi:10.1021/jacs.9b00069 (英语). 
  5. ^ Vogt T., Fitch A. N., Cockcroft J. K. Crystal and Molecular Structures of Rhenium Heptafluoride. Science. 1994, 263 (5151): 1265. PMID 17817431. doi:10.1126/science.263.5151.1265. 
  6. ^ Jacob, E. Jean; Bartell, L.S.J. Electron Diffraction Study of Rhenium Fluorides. II. Structure, Pseudorotation, and Anharmonic Coupling of Modes in ReF7. The Journal of Chemical Physics. 1970, 53 (6): 2235. doi:10.1063/1.1674318. 
  7. ^ 7.0 7.1 A. F. Holleman; Wiberg, Egon; Wiberg, Nils. Inorganic Chemistry. Boston: Academic Press. 2001. ISBN 0-12-352651-5. 
  8. ^ Hwang, I; Seppelt, K. The structures of ReF8 and UF82−. Journal of Fluorine Chemistry. 2000, 102: 69. doi:10.1016/S0022-1139(99)00248-1. 

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