Formation, Structure, and Properties of Nitrosonium and Nitronium Fluorosulfate

Abstract

The reactions of the nitrogen oxides, N20, NO, N203, NOZ(N204), and N205, the oxychlorides ClNO and CINO,, and the oxyanions NO2-and NO3-wlth the fluorosulfonat~ng agents S206Fz and BrOS0,F are studied systematically in regard to the formation of nitrosonium and nitronium fluorosulfate. Complex reactions are found when N203 and N204 are used as substrates, resulting in mixed or impure products. An explanation involving the intermediate oxidation into N 2 0 5 is put forward to explain theThe solid products NOS03F and N02S03F are characterized by powder X-ray analysis, infrared and Raman spectroscopy, and their solutlon behavior in HS03F. Whereas NOS03F has been found to have an orthorhombic lattice, NOzS03F crystallizes in the monoclinic system. Unit cell parameters are reported. The vibrational spectra are interpreted in terms of ionic compounds NOCS03F-and NO*+-S 0 3 F e . The SO?F-anion, however, appears to be perturbed and all the E modes are slightly spllt. No unambiguous evldence for a previously reported non-linear NOz+ cation is found. Force constants for this species are calculated assuming Dm,, symmetry.Both compounds are found to be completely dissociated in HS03F asevidenced by conductometry and 'H and 19F nuclear magnetic resonance (n.m.r.) spectroscopy.

The vibrational spectra of ClF2SbF6, BrF2SbF6, and ClO2SbF6

“…A previously reported value of 350 cm-' found for LiSbF, (15) is not confirmed even though the other assignments agree well. We find v, at 270 cm-' for KSbF, as well as for NO-and NO,SbF, (14).…”

“…The infrared spectrum of ClO,SbF, previously reported by us (9) is now extended down to 250 cm-l. As discussed more fully in another paper (14), principal disagreement in the assignment of v, for the undistorted SbF,-exists. A previously reported value of 350 cm-' found for LiSbF, (15) is not confirmed even though the other assignments agree well.…”

“…A study of a number of related nitrogen oxy and fluoro hexafluoroarsenates and antimonates (14) had established a narrow range for the five i.r. and Raman active fundamentals, some minor discrepancies interpreted as site symmetry effects notwithstanding.…”

Synthetic and Raman spectroscopic study of the fluorosulfates of zinc, cadmium, and mercury

“…The higher frequency band had been assigned as v,, in ionic compounds the asymmetric SO3 bend ( 1 , 7), and this assignment had been aided by an observable but small band splitting (7) and the relative intensities. For the group IIB metal fluorosulfates a rather intense band at -600 cm-' is followed in the Raman spectra by a weaker band at -570 cm-'.…”

The reaction of tetrasulphur tetranitride with bis(fluorosulphuryl) peroxide: the electronic structure of the tetrathiazyl dication

“…The vibrational frequencies of the anion are all comparable to those in the ionic NOS0,F (14), and the weakness of ionic polarization in 1 is attested not only by the small splitting of the E modes (e.g. by 27cm-I for v,(SO,)) but also by the particularly low value of v(SF), characteristic of an isolated S0,F-ion.…”