Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV)
(2017) European Journal of Inorganic Chemistry — p. 2130-2137 (2017)
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- Reactions between XeF2, MnF3 and UV-irradiated elemental F2 in anhydrous HF have yielded [XeF5]2[MnF6] and XeF5MnF5; meanwhile, [XeF5]4[Mn8F36] has been observed as a minor phase upon the crystallization of the product obtained by fluorination of an n(XeF2)/n(MnF3) = 1:3 mixture in the presence of an UV source. The crystal structure of [XeF5]2-[MnF6] is isotypic with the known [XeF5]2[PdF6]. Its asymmetric structural unit consists of two crystallographically unique [XeF5]+ cations and a [MnF6]2– anion. The singlecrystal structure determination of XeF6·2MnF4 reveals that it is better formulated as [XeF5]4[Mn8F36]. Discrete octameric [Mn8F36]4– anions are built from eight MnF6 octahedra, each sharing three vertices, in the shape of a ring, which is Introduction In 1970, Aubert and Cady reported high-temperature fluorinations of a Mn and Xe mixture by elemental fluorine at high pressure.[1] They found that a complex was formed; however, they were not sure about the oxidation state of manganese (III or IV). Six years later, Bohinc et al.[2] reported a much more extensive study on the reactions between MnF2 and excessive XeF6 at 60 °C. The obtained compounds, formulated as 4XeF6·MnF4, 2XeF6 ·MnF4, XeF6 ·MnF4 and XeF6·2MnF4, were characterized by total chemical elemental analysis, IR spectroscopy and magnetic susceptibility measurements. Although different from the previously known cubic [Ti8F36]4– anion. The main structural feature of the anionic part of the crystal structure of [XeF5][MnF5] (determined from both X-ray single-crystal and synchrotron X-ray powder diffraction data) is infinite zigzag chains of distorted MnF6 octahedra that share cis vertices. [XeF5][MnF5] is paramagnetic in the 296–200 K temperature range, with a Curie constant of C = 1.87 emu K mol–1 (μeff = 3.87 μB) and a Curie–Weiss temperature of θ = –9.3 K. Below 100 K, there is weak antiferromagnetic coupling between the MnIV ions, with a coupling constant of J = –1.3 cm–1. Raman spectra showed that [XeF5]2[MnF6] decomposes at ambient temperature in a He–Ne laser beam (power > 1.7 mW) to [XeF5][MnF5], with further decomposition to MnF3.
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Mazej, Z., Goreshnik, E., Jagličić, Z., Filinchuk, Y., Tumanov, N., & Akselrud, L. G. (2017). Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV). European Journal of Inorganic Chemistry, 2130-2137. https://doi.org/10.1002/ejic.201700054 (Original work published 2017)