Syntheses and Structures of Two Dimethyl Diselenide–Diiodine Adducts and the First Well Characterized Diorgano Disulfide–Nitrosonium Adduct

Abstract

The syntheses and crystal structures of two new dimethyl diselenide-iodine adducts are described as well as the synthesis and crystal structure of the first diorgano disulfidenitrosonium adduct. The reaction of the NO + cation with R 2 S 2

XeF2/Fluoride Acceptors as Versatile One‐Electron Oxidants

“…This direct generation of sulfenium ions from disulfides is without alternatives except electro-oxidation. [17,18,32] Whereas diselenides and ditellurides can be oxidized with NO + salts, [29,1,3] dialkyl disulfides and NO + salts form chargetransfer complexes without electron transfer [33] (standard potential of NO + in CH 2 Cl 2 : 1.7 V vs. NHE). [14] It is not known whether the stronger NO 2 + salts can oxidize R 2 S 2 .…”

XeF2/Fluoridakzeptoren als vielseitige Einelektronen‐Oxidationsmittel

“…Mit TTF [13,15,21] und [(FeCpS) 4 ], [16] [17,18,32] alternativlos. Während Diselenide und Ditelluride noch mit NO + -Salzen oxidierbar sind, [29,1,3] entstehen aus Dialkyldisulfiden und NO + -Salzen lediglich Charge-Transfer-Komplexe, ohne dass ein Elektronentransfer stattfindet [33] (Standardpotential von NO + in CH 2 Cl 2 : 1.7 V gegen NHE). [14] Ob die etwas stärkeren NO 2 + -Salze R 2 S 2 oxidieren kçnnen, ist nicht bekannt.…”

NO(HSO4), a Fairly Ionic Solid

“…To that end, it is not the electrostatic surface alone that determines the anion‐binding sites of the nitrosyl cation, but the interaction between filled anion orbitals and the two degenerate LUMOs of the cations supplements the electrostatic attraction. Simple nitrosyl salts thus show a contribution to their bonding that is, to a much more pronounced extent, classified as charge‐transfer adduct formation as in the NO + /disulfide couple …”