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 infrared and Raman spectra of chloryl hexafluoroarsenate have been obtained. The observed vibrations have been interpreted in terms of an ionic compound C10z+AsF6-, where strong cation-anion interaction results in a symmetry lowering of the ion. The compound together with chloryl fluoride produces the chloronium cation C102+(solv) in solution of fluorosulfuric acid. The solvolysis of FC102 is studied by conductometry and 19F nuclear magnetic resonance (n.rn.r.) in order to elucidate the observed anionxation interaction for C1O2AsF6 more fully. 'T n.m.r. studies of FCIO, and related molecules have been used to discuss the bonding in chloronium compounds.

Acidolysis of tetramethylgermane (I) and trimethylchlorogermane (IV) in the sulfonic acids (II) yields the trimethylgermyl sulfonates (III) or the dimethylgermanediyl bissulfonate (V).