AsF5 Research Articles

Intercalation of arsenic pentafluoride in a graphite lattice

Intercalation of arsenic pentafluoride in a graphite lattice

The oxidation of manganese, iron, cobalt, and nickel by the pentafluorides of arsenic and antimony : preparation of some unsolvated metal hexafluoro-arsenates and -antimonates

Oxidation of manganese, iron, and nickel with arsenic pentafluoride in liquid sulphur is a route to Mn(AsF 6) 2, FeF(AsF 6) and NiF(AsF 6) respectively. Cobalt is also oxidised by arsenic pentafluoride but a stable cobalt hexafluroarsenate could not be isolated. Antimony pentafluoride in liquid sulphur dioxide oxidises excess manganese, iron, cobalt and nickel giving Mn(SbF 6) 2, Fe(SbF 6) 2, CoF(SbF 6) and NiSbF 6 2, respectively. The 57Fe Mössbauer Spectra of FeF(AsF 6) and Fe(SbF 6) 2 indicate that both compounds contains six-coordinate iron(II).

The interaction of ClO 2SO 3F with AsF 5 and SbF 5

The interaction of ClO 2SO 3F with AsF 5 and SbF 5

The Preparation and Properties of Complexes of Antimony and Bismuth Trifluorides with Strong Fluoride Acceptors

The reactions of antimony and bismuth trifluorides with the pentafluorides of antimony and arsenic in liquid sulfur dioxide yield the adducts SbF3•SbF5 (type A), SbF3•AsF5, BiF3•3SbF5, and BiF3•AsF5; no adducts of the trifluorides with BF3 were isolated. Antimony metal reacts with excess of antimony pentafluoride and arsenic pentafluoride in liquid sulfur dioxide giving a second form of SbF3•SbF5 (type B) and the same form of SbF3•AsF5 as produced from SbF3, respectively. BiF3•3SbF5 can be formulated as Bi(SbF6)3, but its Raman spectrum indicates the presence of extensive cation–anion fluorine-bridging. Their Raman spectra suggest that BiF3•AsF5, SbF3•AsF5, and SbF3•SbF5 (type B) have similar structures, possibly containing polymeric fluorine-bridged cations, but that SbF3•SbF5 (type A) has a different structure probably like that of AsF3•SbF5. The 121Sb Mössbauer spectra of the SbF3 adducts support the assignment of similar structures to SbF3•AsF5 and SbF3•SbF5 (type B), and the suggestion that SbF3•AsF5 and both forms of SbF3•SbF5 contain antimony (III) fluoro-cations. 19F n.m.r. shows that SbF3 has appreciable solubility in SO2 solutions of SbF5 and indicates the possible formation of "fluxional" SbF2–SbnF5n+1 molecules in SbF3–SbF5 solutions.

The hydrogen fluoride solvent system. Part VI. Solutions of hydrogen cyanide, silver(I) cyanide, and hexacyanoferric(II) acid: formation of the difluoromethylammonium cation

Hydrogen cyanide, a non-electrolyte in anhydrous hydrogen fluoride, is protonated in the presence of boron tri-fluoride and arsenic pentafluoride. Unstable solids believed to be HCNH+BF4– and HCNH+AsF6– have been prepared. In solution in hydrogen fluoride, hydrogen cyanide slowly adds HF to form the cation F2HC·NH3+, which has been isolated as the AsF6– salt. Further slow reaction occurs in solution to form a polymer containing CF2H·NH groups. Conductimetric titrations of silver(I) cyanide and hexacyanoferric(II) acid with BF3 show that neither solute liberates HCN in this solvent; hexacyanoferric(II) acid forms Fe(HCN)62+.

Preparation and crystal structure of the Hg4 2+ ion

The compound Hg4(AsF6)2 containing mercury in the oxidation state of +½ has been obtained from the reaction of mercury with arsenic pentafluoride in liquid SO2; the Hg42+ ion is shown by X-ray methods to be very nearly linear with Hg–Hg distances of 2·57 and 2·70 A.

Cleavage reactions of arsenic trifluoride with element-trimethylsilyl compounds

In the reactions of compounds of the types Me 3SiNR 2, Me 3SiOR, Me 3SiSPh, (Me 3Si) 2NH, (Me 3Si) 2NR, (Me 3SiNMe) 2CO, (Me 3SiO) 2- o-C 6H 4, and (Me 3Si) 3N, with arsenic trifluoride, cleavage of the element-silicon bond was observed. Formation of an arsenic-element bond took place in all cases, and the trimethylsilyl group was released in the form of trimethylfluorosilane. Arsenic pentafluoride reacted in a similar manner but, owing to further reactions (especially reduction of As v → As III) defined products were not normally obtained. Mono-trimethylsilyl-substituted compounds gave rise to the corresponding -AsF 2 derivatives, while some unusual products were obtained from bis- or tristrimethylsilyl precursors. 1H and 19F NMR spectroscopy have been used in the characterization of the products obtained.

A 19F Nuclear Magnetic Resonance Study of Halogen Exchange between Antimony Pentafluoride and Inorganic Chlorides. Complexes of Antimony and Arsenic Pentafluorides with Carbonyl Fluoride

19F nuclear magnetic resonance (n.m.r.) has been used to study the reactions occurring in the systems SbCl5–SbF5–SO2ClF, SO2Cl2–SbF5–SO2ClF, COF2–SbF5–SO2ClF, COF2–AsF5–SO2ClF, and COClF–SbF5–SO2ClF. Ionization occurs in SbCl5–SbF5–SO2ClF, yielding antimony chloro- and chloro-fluorocations and antimony polyfluoroanions. Donor-acceptor complexes are formed between SbF5 and SO2Cl2, COF2 or COClF at low temperatures and also between AsF5 and COF2. In all the complexes the ligand is oxygen-bonded. At higher temperatures halogen exchange and ionization occurs in SO2Cl2–SbF5–SO2ClF and COClF–SbF5–SO2ClF giving SO2ClF and COF2 complexes, respectively, together with antimony cations and polyfluoroanions. The alkyl chloride –SbF5 reaction is also shown to give chlorine-containing cations of antimony.

Reactions of Disulfur Difluoride with Fluorosulfonic Acid, Oleum, Boron Trifluoride, and Arsenic Pentafluoride

Reactions of Disulfur Difluoride with Fluorosulfonic Acid, Oleum, Boron Trifluoride, and Arsenic Pentafluoride

Trifluoromethylsulfur trifluoride adducts. Adducts with phosphorus pentafluoride, boron trifluoride, arsenic pentafluoride, and antimony pentafluoride

Trifluoromethylsulfur trifluoride adducts. Adducts with phosphorus pentafluoride, boron trifluoride, arsenic pentafluoride, and antimony pentafluoride

The +? oxidation state of mercury

The new compound Hg62+(AsF6–)2 containing mercury in the previously unknown oxidation state of +⅓ has been obtained by the reaction of mercury with arsenic pentafluoride in liquid SO2.

Preparation and crystal structure of the Hg3 2+ ion

The new compound Hg32+(AsF6–)2 containing mercury in the oxidation state of +2//3 has been obtained by the reaction of mercury with arsenic pentafluoride in liquid SO2; the Hg32+ ion which is shown, by X-ray methods, to be linear and symmetrical is also obtained when mercury is dissolved in fluorosulphuric acid.

Hydrogen fluoride solvent system. Part III. Solutions of the acids SbF5, AsF5, and PF5. Evidence for the As2F11 ? ion

Cryoscopic measurements on solutions of antimony pentafluoride in HF confirm that it is a strong 1 : 1 electrolyte in dilute solutions. Cryoscopic and conductimetric measurements show that arsenic pentafluoride dissolves to form the strong electrolyte H2F+As2F11–. The dimeric anion As2F11– has been isolated as the tetraethylammonium salt. Phosphorus pentafluoride appears to be a non-electrolyte in this solvent.

Exchange Reactions of the t-Butyl Cation

The exchange reaction between t-butyl cation and isobutane in sulfur dioxide solution is first order in both species with Ea = 3.6 kcal/mole and ΔS*298 = −27 e.u. No reaction is observed, under these conditions, between the t-butyl cation and n-butane or neopentane. In a similar system the isopropyl chloride – arsenic pentafluoride complex reacts rapidly with n-butane to yield propane and the t-butyl cation, but does not react with neopentane or cyclopropane. An exchange reaction was also observed between the isopropyl chloride – arsenic pentafluoride complex and propane.

Nuclear magnetic resonance investigation of complexes formed by arsenic pentafluoride and some very weak bases

Nuclear magnetic resonance investigation of complexes formed by arsenic pentafluoride and some very weak bases

Molecular structures of arsenic trifluoride and arsenic pentafluoride as determined by electron diffraction

Molecular structures of arsenic trifluoride and arsenic pentafluoride as determined by electron diffraction

Infrared Spectra of Matrix-Isolated Antimony and Arsenic Pentafluorides

The infrared spectra of SbF5 and AsF5 suspended in argon and neon matrices have been recorded between 4000 and 100 cm−1. The spectra of SbF5 and AsF5 are radically different and show that monomeric SbF5 belongs to symmetry group C4υ rather than to group D3h. The spectral effects induced by forming solid SbF5 from the monomers are understood in terms of associations through Sb–F–Sb fluorine bridge bonds. The behavior is compared with that observed previously for SF4. No evidence for fluorine bridging occurs with AsF5.

The +1 oxidation state of antimony

The reaction of antimony with arsenic pentafluoride in liquid SO2 produces a compound formulated as (Sbnn+)(AsF6–)n.

The compounds S8(AsF6)2 and S16(AsF6)2

From the reaction between sulphur and arsenic pentafluoride the new compounds S8(AsF6)2 and S16(AsF6)2 have been isolated and identified.

Reactions of oxides of nitrogen with the Group V pentafluorides and stannic fluoride

The pentafluorides of phosphorus, arsenic, and antimony have been treated with inter alia, nitric oxide, dinitrogen trioxide, nitrogen dioxide, and dinitrogen pentoxide, and stannic fluoride has been treated with nitrogen dioxide.Nitric oxide does not combine chemically with phosphorus pentafluoride, and yields only a single involatile phase, NOAsF6, with arsenic pentafluoride. The other reactions yield complex mixtures, all of which contain nitrosonium and/or nitronium salts. Evidence is presented for the formation of complex oxyfluoride species containing anions of general formula [MOF4]–(M = P, As, Sb). The [Sb2F11]– anion is frequently formed in reactions involving antimony pentafluoride.Antimony pentafluoride reacts with oxides of nitrogen in the liquid phase to form nitrito- or nitrato-fluorides, and stannic fluoride also forms a nitrato-fluoride when treated with liquid dinitrogen tetroxide.