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Fluorosulfates of silver, ruthenium, and osium

University of British Columbia

A number of synthetic routes to silver(II) fluorosulfate, Ag(SO₃F)₂, were systematically explored. The most suitable and versatile route was found to be the oxidation of silver metal by a solution of bisfluorosulfuryl peroxide, S₂0₆F₂, in fluorosulfuric acid, HSO₃F, according to: [chemical reaction] Additional methods which were found to be suitable involved the oxidation of a wide variety of silver(I) compounds such as Ag₂0 or AgSO₃F by S₂O₆F₂' or the insertion of S0₃ into AgF₂. Structural conclusions on Ag(S0₃F)₂ and the other compounds synthesized subsequently were based on the vibrational, electronic and electron spin resonance spectra, as well as on magnetic susceptibility measurements made between 300 and 77 K. Ag(S0₃F) ₂was found to be a true compound of divalent silver, with the Ag²⁺ ions in either square planar or tetragonally elongated octahedral environment. The only other example of a binary silver(II) compound is AgF₂. and characterized. The reactions of bromine(I) fluorosulfate with metallic silver and other silver(I) substrates resulted in a mixed valence complex Ag[sup I]Ag[sup II](SO₃F)₄ . Its potassium analogue K₂AgCSO₃F)₄, as well as two hexakisfluorosulfato- metallate (IV) complexes AgPt[sup= IV] (SO₃F)₆ , and AgSn[sup= IV] (SO₃F)₆, and the N-donor ligand complex [Ag(bipy)₂l (SO₃F)₂ (i-n which bipy = 2,2'-bipyridine) were also synthesized. The attempt to synthesize a silver(III) fluorosulfato complex by direct insertion of SO₃ into CsAgF₄ resulted in the fluorination of SO₃, to give S₂O₆F₂ and CsAg(SO₃F)₃. Finally, the solvolysi of Ag(SO₃F)₂ in trifluoromethylsulfuric acid, HSO₃CF₃, allowed its conversion into Ag(SO₃F₃). The principal synthetic route, the oxidation of metal by S₂O₆F₂ solutions in HSO₃F, was found to be useful in the preparation of Ru(SO₃F)₃. Ruthenium was also found to form a number of anionic derivatives with the metal in the +3 or +4 oxidation state, as in M[Ru(SO₃F)₄] with M = Cs⁺, ClO₂⁺ ; M₂[Ru(SO₃F)₆ with M = Cs⁺, K⁺; and Cs[Ru(SO₃F)₅]. Two different forms of Os(SO₃F)₃ were found. Initial oxidation of osmium metal with S₂O₆F₂ yielded the bright green a-Os(SO₃F)₃, which was converted to the light green β-form on long standing in S₂O₆F₂.

Text

2010-03-26

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http://hdl.handle.net/2429/22540

Chemistry

University of British Columbia

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