Xenon–Nitrogen Chemistry: Gas‐Phase Generation and Theoretical Investigation of the Xenon–Difluoronitrenium Ion F<sub>2</sub>NXe<sup>+</sup>

Operti, Lorenza; Ragazzoni, Roberto; Turco, Francesca; Borocci, Stefano; Giordani, Maria; Grandinetti, Felice

doi:10.1002/chem.201101395

Cited by 40 publications

(20 citation statements)

References 88 publications

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“…Moreover,n eutraln oble gas compounds, through insertion of an Ng atom into nitrogen monofluoride (NF) and phosphorus monofluoride (PF), have not been investigated so far,a lthough the [FÀXeÀNÀF] + ion in the triplet state has been reported recently. [26] The existence of NNg + speciesh ad also been reported earlier. [38] Consequently, it is quite natural to expect that the NNg + ions could be stabilized in the presence of an anion such as F À ,a nalogous to the stabilization of ArH + in the presence of F À .…”

Section: Introductionsupporting

confidence: 57%

Prediction of a Neutral Noble Gas Compound in the Triplet State

Manna

Ghosh

Ghanty

2015

Chemistry A European J

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Discovery of the HArF molecule associated with H-Ar covalent bonding [Nature, 2000, 406, 874-876] has revolutionized the field of noble gas chemistry. In general, this class of noble gas compound involving conventional chemical bonds exists as closed-shell species in a singlet electronic state. For the first time, in a bid to predict neutral noble gas chemical compounds in their triplet electronic state, we have carried out a systematic investigation of xenon inserted FN and FP species by using quantum chemical calculations with density functional theory and various post-Hartree-Fock-based correlated methods, including the multireference configuration interaction technique. The FXeP and FXeN species are predicted to be stable by all the computational methods employed in the present work, such as density functional theory (DFT), second-order Møller-Plesset perturbation theory (MP2), coupled-cluster theory (CCSD(T)), and multireference configuration interaction (MRCI). For the purpose of comparison we have also included the Kr-inserted compounds of FN and FP species. Geometrical parameters, dissociation energies, transition-state barrier heights, atomic charge distributions, vibrational frequency data, and atoms-in-molecules properties clearly indicate that it is possible to experimentally realize the most stable state of FXeP and FXeN molecules, which is triplet in nature, through the matrix isolation technique under cryogenic conditions.

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Section: Introductionsupporting

confidence: 57%

Prediction of a Neutral Noble Gas Compound in the Triplet State

Manna

Ghosh

Ghanty

2015

Chemistry A European J

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“…These new findings began to change people's perception of the chemical bonding ability of noble gases. Subsequently, many experimental scientists contributed to new Ng compounds, and with the rapid development of precision computation technology, a large number of thermodynamically and kinetically stable Ng compounds have been theoretically predicted including HNgY (Ng = Ar, Kr, Xe, Y = electronegative chemical groups), HXeCCH (C nv ), HXeCC (C nv ), and HXeCCXeH (D 2h ), and B n Ng n (n‐2)+ and B 3 N 3 NgR 6. And the most recently detected Ng compound is Na 2 He, a stable compound of helium and sodium, which was first predicted using the ab initio evolutionary algorithm universal structure prediction: evolutionary xtallography and subsequently was synthesized at high pressure in a diamond anvil cell by Xiao Dong and coworkers …”

Section: Introductionmentioning

confidence: 99%

Theoretical predictions of the nitrogen heterocyclic compounds with metal and noble gas (metal = Cu, Ag, Au)

Wen

2019

Int J of Quantum Chemistry

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Here, we report a new type of Ng-containing compounds formed between the Ng-M group and nitrogen heterocyclic compounds, (CH 2 ) n HNCuNg + (n = 2, 3), (CH) 4 NMNg, and (CH) 5 NCuNg + (M = Cu, Ag, Au; Ng = Ar, Kr, Xe). Quantum chemistry computations were carried out to optimize their geometric structures and calculate the dissociation energies, dissociation enthalpy, and dissociation free energy change. The stability of these Ng-bonding complexes was inspected by investigating the three dissociation processes of the these compounds into (a) Ng, M, and nitrogen heterocycle C n N; (b) C n N + MNg + ; and (c) C n NM + Ng, which are all endothermic and nonspontaneous, these dissociation processes are also turned out to be endergonic in nature at standard state. The natural bond orbital, atoms in molecules, and energy decomposition analysis based on the molecular wavefunction show that the M-Ng and M-N bonds have some covalent and electrostatic characters. K E Y W O R D S AIM, EDA, NBO, Ng-containing compounds, nitrogen heterocyclic 1 | INTRODUCTION The noble gas (Ng) atoms are in general inert and rarely participate in chemical reactions because of their filled outer shell electronic structure.So the noble gas chemical bonding has been a mystery attracting chemists' attention. However, Pauling [1] predicted at the earliest the possible existence of the noble gas compounds KrF 6 , XeF 6 , XeF 8 , xenic acid HXeO 6 , and perxenate Ag 4 XeO 6 in 1933. Until 1962, Bartlett [2] synthesized the first Xe compound Xe + [PtF 6 ] − , which opens up a new field of research for the scientific community. In the following decades, several stable Ng compounds have been synthesized. [3][4][5][6][7] These new findings began to change people's perception of the chemical bonding ability of noble gases. Subsequently, many experimental scientists contributed to new Ng compounds, [8][9][10][11][12][13][14][15][16][17][18][19] and with the rapid development of precision computation technology, a large number of thermodynamically and kinetically stable Ng compounds have been theoretically predicted including HNgY [20][21][22][23] (Ng = Ar, Kr, Xe, Y = electronegative chemical groups), HXeCCH (C nv ), HXeCC (C nv ), and HXeCCXeH (D 2h ), [24] and B n Ng n (n-2)+ [25] and B 3 N 3 NgR 6.[26] And the most recently detected Ng compound is Na 2 He, a stable compound of helium and sodium, which was first predicted using the ab initio evolutionary algorithm universal structure prediction: evolutionary xtallography and subsequently was synthesized at high pressure in a diamond anvil cell by Xiao Dong and coworkers. [27] The noble metal atoms (Cu, Ag, Au) are also relatively chemically stable, the bonding between inert gas and noble metal atoms may be arduous in the theory of chemical bonds. Nevertheless, in 1995, Pyykkö [28] first predicted the possible existence of the NgAu + and NgAuNg + species, and 3 years later, Xe analogues were detected in mass spectrometry. [29] There are some controversies about the nature of the bond between inert gases a...

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“…On the other hand, although the compounds with Ng−N bonds are outnumbered with respect to the former one, the first Xe−N compound, FXeN(SO 2 F) 2 was observed spectroscopically in 1974 . It was followed by [(FSO 2 ) 2 NXe] 2 F + AsF 6 − , Xe[N(SO 2 F) 2 ] 2 , [XeN(SO 2 F) 2 ] + , Xe[N(SO 2 CF 3 ) 2 ] 2 , XeF + adducts with HCN, alkylnitriles, pentafluorobenzenenitrile, perfluoroalkylnitriles, perfluoropyridines, thiazyl trifluoride, and s‐trifluorotriazine, FXe(N 3 ), FXe(NCO), F 5 TeN(H)Xe + , F 5 SN(H)Xe + , C 6 F 5 XeNCCH 3 + , F 4 SNXe + , F 2 NXe + , and XeNO 3 + . Computational predictions were also made for Xe inserted PF and NF species as well as for XeNO 2 − and XeNO 3 − systems .…”

Section: Introductionmentioning

confidence: 99%

Stable NCNgNSi (Ng=Kr, Xe, Rn) Compounds with Covalently Bound C‐Ng‐N Unit: Possible Isomerization of NCNSi through the Release of the Noble Gas Atom

Pan

Jana

Ravell

et al. 2018

Chemistry A European J

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Although the noble gas (Ng) compounds with either Ng-C or Ng-N bonds have been reported in the literature, compounds containing both bonds are not known. The first set of systems having a C-Ng-N bonding unit is predicted herein through the analysis of stability and bonding in the NCNgNSi (Ng=Kr-Rn) family. While the Xe and Rn inserted analogues are thermochemically stable with respect to all dissociation channels, but for the one producing CNSiN and free Ng, NCKrNSi has another additional three-body dissociation channel, NCKrNSi→CN+Kr+NSi, which is exergonic by -9.8 kcal mol at 298 K. This latter dissociation can be hindered by lowering the temperature. Moreover, the NCNgNSi→Ng+CNSiN dissociation is also kinetically prohibited by a quite high free energy barrier ranging from 25.2 to 39.3 kcal mol , with a gradual increase in going from Kr to Rn. Therefore, these compounds are appropriate candidates for experimental realization. A detailed bonding analysis by employing natural bond orbital, electron density, energy decomposition, and adaptive natural density partitioning analyses indicates that both Ng-N and C-Ng bonds in the title compounds are covalent in nature. In fact, the latter analysis indicates the presence of delocalized 3c-3e σ-bond within the C-Ng-N moiety and a totally delocalized 5c-2e σ-bond in these compounds. This is an unprecedented bonding characteristic in the sense that the bonding pattern in Ng inserted compounds is generally represented as the presence of covalent bond in one side of Ng, and the ionic interaction in the other side. Further, the dissociation of Ng from NCNgNSi facilitates the formation of a higher energy isomer of NCNSi, CNSiN, which cannot be formed from bare NCNSi as such, because of the very high free energy barrier associated with the isomeric transformation. Therefore, in the presence of Ng atoms it might be possible to detect the high energy isomer.

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

Cited by 40 publications

References 88 publications

Prediction of a Neutral Noble Gas Compound in the Triplet State

Prediction of a Neutral Noble Gas Compound in the Triplet State

Theoretical predictions of the nitrogen heterocyclic compounds with metal and noble gas (metal = Cu, Ag, Au)

Stable NCNgNSi (Ng=Kr, Xe, Rn) Compounds with Covalently Bound C‐Ng‐N Unit: Possible Isomerization of NCNSi through the Release of the Noble Gas Atom

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

Cited by 40 publications

References 88 publications

Prediction of a Neutral Noble Gas Compound in the Triplet State

Prediction of a Neutral Noble Gas Compound in the Triplet State

Theoretical predictions of the nitrogen heterocyclic compounds with metal and noble gas (metal = Cu, Ag, Au)

Stable NCNgNSi (Ng=Kr, Xe, Rn) Compounds with Covalently Bound C‐Ng‐N Unit: Possible Isomerization of NCNSi through the Release of the Noble Gas Atom

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