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Issue 29, 2013
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AgS2O6CF3: the first trifluoromethylsulfonylsulfate(VI)

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Abstract

We describe the synthetic route towards a novel class of salts, trifluoromethylsulfonylsulfates, as exemplified by the silver(I) derivative (AgS2O6CF3). Formation proceeds via direct reaction between a triflate precursor, AgSO3CF3, and SO3. The title compound crystallizes in the P21/c unit cell with a = 5.15746(14) Å, b = 25.8563(9) Å, c = 5.53970(14) Å and β = 101.1749(19)°. The structure is layered with the puckered [AgS2O6] 2D sheets; the terminal CF3 groups are separated by the van der Waals gap, as seen also for related metal triflates. The compound is very fragile thermally and it decomposes endothermally to AgSO3CF3 with concomitant evolution of SO3 even at 65 °C or upon grinding in an agate mortar; thus it may serve as a solid store of – otherwise volatile and corrosive – SO3. The IR and Raman spectra of AgS2O6CF3 have been tentatively assigned based on similarities to those of related Ag2S2O7 and AgSO3CF3 and phonon calculations. Synthesis and properties of KS2O6CF3 are also briefly described.

Graphical abstract: AgS2O6CF3: the first trifluoromethylsulfonylsulfate(vi)

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Publication details

The article was received on 21 Feb 2013, accepted on 12 Apr 2013 and first published on 07 May 2013


Article type: Paper
DOI: 10.1039/C3DT50473E
Citation: Dalton Trans., 2013,42, 10417-10423
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    AgS2O6CF3: the first trifluoromethylsulfonylsulfate(VI)

    P. J. Malinowski, M. Derzsi and W. Grochala, Dalton Trans., 2013, 42, 10417
    DOI: 10.1039/C3DT50473E

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