Xenon–Nitrogen Chemistry: Gas-Phase Generation and Theoretical Investigation of the Xenon–Difluoronitrenium Ion F2NXe+

✍ Scribed by Prof. Lorenza Operti; Prof. Roberto Rabezzana; Dr. Francesca Turco; Dr. Stefano Borocci; Dr. Maria Giordani; Prof. Felice Grandinetti

• Book ID: 101840400
• Publisher: John Wiley and Sons
• Year: 2011
• Tongue: English
• Weight: 369 KB
• Volume: 17
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.201101395

✦ Synopsis

Abstract

The xenon–difluoronitrenium ion F~2~NXe^+^, a novel xenon–nitrogen species, was obtained in the gas phase by the nucleophilic displacement of HF from protonated NF~3~ by Xe. According to Møller–Plesset (MP2) and CCSD(T) theoretical calculations, the enthalpy and Gibbs energy changes (Δ__H__ and Δ__G__) of this process are predicted to be −3 kcal mol^−1^. The conceivable alternative formation of the inserted isomers FNXeF^+^ is instead endothermic by approximately 40–60 kcal mol^−1^ and is not attainable under the employed ion‐trap mass spectrometric conditions. F~2~NXe^+^ is theoretically characterized as a weak electrostatic complex between NF~2~^+^ and Xe, with a XeN bond length of 2.4–2.5 Å, and a dissociation enthalpy and free energy into its constituting fragments of 15 and 8 kcal mol^−1^, respectively. F~2~NXe^+^ is more fragile than the xenon–nitrenium ions (FO~2~S)~2~NXe^+^, F~5~SN(H)Xe^+^, and F~5~TeN(H)Xe^+^ observed in the condensed phase, but it is still stable enough to be observed in the gas phase. Other otherwise elusive xenon–nitrogen species could be obtained under these experimental conditions.