title: Xenon-nitrogen chemistry: gas-phase generation and theoretical investigation of the xenon-difluoronitrenium ion F2N-Xe+.
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 (ΔH and ΔG) 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.
authors.affiliation: Dipartimento di Chimica Generale e Chimica Organica, Università degli Studi di Torino, Italy.
authors.forename: Lorenza
authors.initials: L
authors.lastname: Operti
authors.forename: Roberto
authors.initials: R
authors.lastname: Rabezzana
authors.forename: Francesca
authors.initials: F
authors.lastname: Turco
authors.forename: Stefano
authors.initials: S
authors.lastname: Borocci
authors.forename: Maria
authors.initials: M
authors.lastname: Giordani
authors.forename: Felice
authors.initials: F
authors.lastname: Grandinetti
mesh_terms: D005740:Gases / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D008962:Models, Theoretical; D009584:Nitrogen / Q000737:chemistry*; D013816:Thermodynamics; D014978:Xenon / Q000737:chemistry*
chemical_list: D005740:Gases; D007477:Ions; D014978:Xenon; D009584:Nitrogen