New evidence in an old case: the question of chromium hexafluoride reinvestigated.
New evidence in an old case: the question of chromium hexafluoride reinvestigated.
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旧案新证据：六氟化铬问题再查
DOI：
10.1021/ic500651r
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发表时间：
2014
影响因子：
4.6
通讯作者：
S. Riedel
中科院分区：
文献类型：
--
作者：
T. Schlöder;F. Brosi;B. J. Freyh;T. Vent-Schmidt;S. Riedel
六氟化铬分子是否已经合成和表征的问题已经在文献中被广泛讨论，尽管做出了许多努力，但仍然不能毫无疑问地回答。新的基质隔离实验现在可以显示，与最先进的量子化学计算一起，先前在惰性气体基质中分离的化合物是CrF5而不是CrF6。基质红外光谱中的新谱带可归属于Cr2F10二聚体，并且在光谱中发现了CrF5在紫外光照射下的光解或可逆激发的证据。然而，即使CrF6在环境条件下不稳定，也不能完全排除在高压釜反应中在高氟压力下形成CrF6。
The question of whether or not the chromium hexafluoride molecule has been synthesized and characterized has been widely discussed in the literature and cannot, in spite of many efforts, yet be answered beyond doubt. New matrix-isolation experiments can now show, together with state-of-the-art quantum-chemical calculations, that the compound previously isolated in inert gas matrixes, was CrF5and not CrF6. New bands in the matrix IR spectra can be assigned to the Cr2F10dimer, and furthermore evidence was found in the spectra for a photodissociation or reversible excitation of CrF5under UV irradiation. However, even if CrF6is not stable at ambient conditions, its formation under high fluorine pressures in autoclave reactions cannot be excluded completely.