The fluoro(hydrogen cyanide)xenon(II) cation. Preparation of HC.tplbond.NXeF+AsF6-: a multinuclear magnetic resonance and Raman spectroscopic study

Abstract

The XeF+ or Xe2F,+ cations react with HC=N in anhydrous HF solvent to give the Lewis acid-base adduct cation HC=NXeF+. The HC=NXeFt cation has been characterized in HF and BrF, solvents by Iz9Xe, I9F, 14315N, I3C, and 'H NMR spectroscopy and has been characterized as its AsFc salt in the solid state by low-temperature Raman spectroscopy. The scalar couplings, IJ(lZ9Xe-l4N), zJ(129Xe-13C), and 3J(129Xe-'H), represent the first examples of couplings observed between these nuclides. The vibrational assignments of the v(Xe-N) stretching and b(XeNC) and b(FxeN) bending modes have been aided by obtaining Raman spectra for natural-abundance 15N-and I3CC-enriched HC=NXeFAsF6-. The solution NMR and low-temperature Raman spectroscopic studies are consistent with a linear C, , structure for the HCSNXeF' cation. The vibrational data together with the NMR chemical shifts indicate that the Xe-N bond is weakly covalent and are in agreement with recent theoretical calculations. NMR spectroscopic studies also show that solutions of HeNXeF+AsF6in HF are extensively solvolyzed to give equilibrium concentrations of the HC=NH+ cation and XeF2.

Reaction of [Xe-F]+ with HI

“…No resonance was found in the range of ‫0001ם‬ to ‫0002מ‬ ppm, indicating that all [XeF][AsF 6 ] had reacted yielding exclusively xenon-free reaction products (cf. d 129 Xe[XeF] ‫ם‬ ‫ס‬ ‫368מ‬ ppm) [9].…”

Nature of the XeVI−N Bonds in F6XeNCCH3and F6Xe(NCCH3)2and the Stereochemical Activity of Their Xenon Valence Electron Lone Pairs

“…[8] Until the syntheses and characterizationo fF 6 XeNCCH 3 and F 6 Xe(NCCH 3 ) 2 ·CH 3 CN, [1] the occurrence of XeÀNb onds had been limited to the + 2a nd + 4o xidations tates of xenon. A considerable number of Xe II species, in which xenon is bonded to sp-, sp 2 -, and sp 3 -hybridized nitrogen, are known.M ost belong to aw eakly bondedc lass of [XeF] + adducts.T hose that exhibit formal nitrogen sp hybridization are the [XeF] + adducts of NSF 3 (thiazyl trifluoride), [9] HCN, [10,11] alkylnitriles, [10] pentafluorobenzenenitrile, [10] perfluoroalkylnitriles, [10,12] and the [C 6 F 5 Xe]…”

Xenon–Nitrogen Chemistry: Gas‐Phase Generation and Theoretical Investigation of the Xenon–Difluoronitrenium Ion F2NXe+

“…The Xe À N cations can be in turn divided into two groups. The first one includes species that arise from the interaction of the Lewis acid XeF + with Lewis nitrogen bases such as RÀCN (R=H, CH 3 , CH 2 F, C 2 H 5 , CF 3 , C 2 F 5 , C 3 F 7 , C 6 F 5 ), [26,28,29] perfluoropyridines, [27] s-trifluorotriazine, [28] and F 3 SN. [31] In these XeF + complexes, the xenonnitrogen interaction is relatively tight, and the observed Xe À N distances range around 2.2-2.3 .…”

“…These structural differences reflect xenon-nitrogen interactions of different character. In particular, whereas F 2 NÀXe + is a weak electrostatic complex, the theoretical charges, valencies, and bond orders of [31] and RCNÀXeF + (R=H, CH 3 , tBu), [26,29,34] the XeÀN bond lengths of which have been measured in the solid state as 2.235, [34] 2.179, [34] and 2.212, [34] respectively. Even though these values can be somewhat affected by the AsF 6 À counteranion, they are undoubtedly shorter than F 2 N À Xe + .…”