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Preparation and Crystal Structure of the Paramagnetic Solid AsF6: Implications for the Indentity of

DOI: 10.1039/DT9920001563

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1563 - 1572 (1992)

Update date:2022-07-30

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Authors:

Cameron, T. StanleyCameron, T. Stanley

Haddon, Robert C.Haddon, Robert C.

Mattar, Saba M.Mattar, Saba M.

Parsons, SimonParsons, Simon

Passmore, JackPassmore, Jack

Ramirez, Arthur P.Ramirez, Arthur P.

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Article abstract of DOI:10.1039/DT9920001563

4,5-Bis(trifluoromethyl)-1,2,3-trithiolylium hexafluoroarsenate, which contains the 7? radical cation, the first example of a cationic carbon-sulfur heterocycle, has been prepared and characterised.It was prepared as a purple solid in 90 percent yield by the reaction of F3CCCCF3 with a 1:1 mixture of S4(AsF6)2 and S8(AsF6)2 in SO2 at 50 deg C for 2 weeks.Small amounts of a homopolyatomic sulfur cation (probably S82+) were removed by work-up with fresh F3CCCCF3 and AsF5 in SO2 at 50 deg C for 8d.The AsF6 was characterised in the solid state by chemical analyses, IR, mass spectrometry and X-ray crystallography.The crystal structure consists of layers containing both monomeric, planar radical cations and AsF6- anions .A powder photograph of the bulk product correlated with the single-crystal data, and a variable-temperature magnetic susceptibility study indicated that AsF6 is a paramagnetic solid, exhibiting oridinary Curie-Weiss behaviour, μ = 1.68, Θ = -0.6 K (μ = 2.1 in SO2 solution at room temperature).The ESR spectrum of in SO2 is identical to that previously reported for , which suggested that spectra long assigned to 1,2-dithiete cations are in fact due to 1,2,3-trithiolium cations.This is supported by the ESR spectrum of , which consisted of a singlet at g = 2.017, with two sets of 33S satellites in a 2:1 intensity ratio, with very similar 33S coupling constants (8.0 and 8.9 G).The salt AsF6 is reduced by KI to give a mixture of neutral cyclic polysulfides including (43percent) and the previously unknown (23percent).Attempts to oxidise with AsF5 were unsuccessful.

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Product name:1,4-Dithiin, 2,3,5,6-tetrakis(trifluoromethyl)-

Cas No:654-60-4

654-60-4

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