H2NO2+ ions in the gas phase: a mass spectrometric and post-SCF ab initio study

Petris, Giulia de; Marzio, Annito Di; Grandinetti, Felice

doi:10.1021/j100177a033

Cited by 33 publications

(25 citation statements)

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“…The choice has been suggested by the consideration that the results from this approach are independent of the possible changes undergone by the accepted values of certain reference data, such as the PA value of NH 3 , utilized in other indirect approaches. Furthermore, the value chosen agrees within 1 kcal⅐mol Ϫ1 with the BE reported from an ab initio calculation performed at the MP4(SDTQ)͞͞6-311G**͞ MP2(FU)͞͞6-31G** ϩ ZPE (MP2(FU)͞6-31G**) level of theory (27). Anchoring the relative scale of Fig.…”

Section: Resultssupporting

confidence: 81%

“…In conclusion, as recently suggested by other authors (38), it appears that the absolute anchor of the Reents and Freiser scale needs to be revised. On the basis of its direct, more reliable measurement (26), whose result agrees with that of a high-level theoretical approach (27), it appears that the choice of the H 2 O-NO ϩ BE as the absolute reference standard is to be preferred, and it is reassuring that it leads to NO ϩ BEs of various molecules in excellent agreement with those from high-level ab initio calculations. Thus, the NO ϩ BE of methanol has been computed to be 25.3 kcal⅐mol Ϫ1 (39), that of oxirane 27.3 kcal⅐mol Ϫ1 (31), and that of acetaldehyde 27.9 kcal⅐mol Ϫ1 (32).…”

Section: Discussionsupporting

confidence: 55%

“…The NO ϩ BEs are in most cases considerably larger, owing again to the smaller size, the higher charge density, and the smaller ion-neutral separation that characterize NO ϩ complexes with respect to their NO 2 ϩ counterparts. Furthermore, at variance with NO 2 ϩ , NO ϩ does not appear to undergo energetically unfavorable deformation upon association with the ligand-i.e., the NOO equilibrium bond length does not change appreciably in passing from free NO ϩ to the H 2 O-NO ϩ complex (27). The larger H 2 O-NO 2 ϩ separation (36) reflects the reluctance of NO 2 ϩ to form tightly bound complexes, where the close approach to the nucleophilic center entails the deformation of the cation.…”

Section: Discussionmentioning

confidence: 99%

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Gas-phase NO ⁺ affinities

Cacace

Petris²,

Pepi³

1997

Proc. Natl. Acad. Sci. U.S.A.

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A scale of relative gas-phase NO ؉ binding energies (BEs) ؉ BE of thymine, the only one accessible to direct measurement, amounts to 35.6 ؎ 2 kcal⅐mol ؊1 , which underlines the predictive value of the correlation. This study reports the second successful extension of the kinetic method to the evaluation of the absolute BEs of polyatomic cations, following our recent application to the strictly related NO 2 ؉ ion.The chemistry of the nitryl ion, NO ϩ , is the focus of active interest, recently heightened by the extraordinary multiplicity of roles currently attributed to NO. Nitryl ion, its salts and carriers, are long known as effective reagents in electrophilic nitrosation, whose study is the subject of continuing interest (refs. 1-4 and references cited in ref.2), in particular as concerns the formation of nitrosoamines (5, 6). Passing to atmospheric chemistry, the low ionization potential of NO makes NO ϩ an effective ''charge sink'' in ionized air, and the promoter of a reaction chain eventually leading to hydratedproton clusters (7,8). As the consequence, complexation of NO ϩ by H 2 O and other atmospheric species (N 2 , CO 2 , O 2 ) has a direct bearing on the chemistry of the ionospheric D region (9-11) and of the middle atmosphere (12). The biological and physiological significance of NO ϩ and of its complexes has received much attention, in connection with the recognized impact on human health of a variety of compounds important for dietary or environmental reasons, including nitrites, Nnitrosoamines, NO x oxides, etc. (13-15). For example, it has been suggested that NO ϩ , or some NO ϩ sources present in biological systems, can be involved in the neurotoxic and neuroprotective actions of NO (16,17) as well as in the nitrous acid-promoted crosslinking of DNA, a problem of considerable current interest (18,19). Finally, the use of NO ϩ as a reagent has a considerable potential for trace gas analysis (20).A quantitative knowledge of the interactions of NO ϩ with neutral ligands is central to the understanding and modelling of important problems in many research fields. This strongly suggests a systematic study of the binding energies (BEs) of the nitryl cation to representative ligands, to be carried preferably in the gas phase, to obtain results of general validity, unaffected by specific ion-solvent interactions and hence more directly comparable to those from theoretical approaches and more widely useful for modelling purposes. The interest of the problem was perceived as early as in 1980 by Reents and Freiser (21), who measured the NO ϩ BE to 28 ligands by ion cyclotron resonance (ICR) mass spectrometry. In view of the current upsurge of interest in the NO ϩ complexes, we have undertaken a systematic study aimed at the revision of the NO ϩ BE scale, taking into account the changes undergone in the meantime by certain reference standards used in the early study and the availability of new experimental tools. However, the principal motivation of this work is to be found in the attempt to exten...

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Section: Resultssupporting

confidence: 81%

Section: Discussionsupporting

confidence: 55%

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Gas-phase NO ⁺ affinities

Cacace

Petris²,

Pepi³

1997

Proc. Natl. Acad. Sci. U.S.A.

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“…According to a recent ab initio study (44), the monomer separation amounts to 2.20 A in the H2O-NOI complex vs. the 2.50-A separation in the H2O-NO' complex, which entails a considerably smaller electrostatic stabilization of the latter.…”

Section: Methodsmentioning

confidence: 96%

Gas-phase nitronium ion affinities.

Cacace

Petris

Pepi

et al. 1995

Proc. Natl. Acad. Sci. U.S.A.

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Evaluation of nitronium ion-transfer equilibria, L1NO' + L2 = L2NO' + L1 (where L1 and L2 are ligands 1 and 2, respectively) by Fourier-transform ion cyclotron resonance mass spectrometry and application of the kinetic method, based on the metastable fragmentation of L1(NO+)L2 nitronium ion-bound dimers led to a scale of relative gas-phase nitronium ion affinities. ligands, aimed at the construction of a gas-phase nitronium ion-affinity scale.To this end, we have applied the Fourier-transform ion cyclotron resonance mass spectroscopy equilibrium method largely used in proton affinity (PA) measurements (34) to NO' transfer reactions and extended the kinetic method, so far used exclusively in PA and gas-phase acidity determinations (35,36), to nitronium ion-bound dimers. MATERIALS AND METHODSAll chemicals were obtained as research-grade products from Aldrich and were used without further purification. The gases were purchased from Matheson with a stated purity >99.95 mol %, except NO2, for which purity was >99.5 mol %, and were used L,NO+ + L2 = L2NO2 + Ll, [1] allows direct determination of the corresponding free energy change, AG', provided that the equilibrium constant can be accurately measured, which requires attainment of true equilibrium, unperturbed by significant side reactions. In the specific application, CH3O(NO2)2, the nitrating reagent, is prepared in the external chemical ionization source of a Fourier transform ion cyclotron resonance mass spectrometer and driven into the resonance cell, where it nitrates both ligands, present in a known concentration ratio. One of the nitrated complexes is isolated by selective-ejection techniques and allowed to equilibrate in the mixture of the ligands. Application of the method is prevented in many cases by incursion of fast proton-transfer reactions that perturb the equilibrium-e.g., the nitronium ion transfer, [C2H5OH-NO2]+ + NH3 = [H3N-NO2]+ + C2H5OH, [la] undergoes competition by proton transfer to ammonia from both nitrated complexes, which react as the conjugate acids of ethyl nitrate and of nitramide. Furthermore, in the case of ligands of low ionization potential the study of equilibrium 1 Abbreviations: PA, proton affinity; BE, binding energy; RP, reference pair; MIKE, mass analyzed ion kinetic energy. tTo whom reprint requests should be addressed.The publication costs of this article were defrayed in part by page charge payment. This article must therefore be hereby marked "advertisement" in accordance with 18 U.S.C. §1734 solely to indicate this fact. 8635

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“…Gaseous H 2 O ϩ NO cations have been obtained by chemical ionization and various reactions have been successfully employed for their preparation, e.g., the addition of nitrosonium cation on neutral water, or the ethene loss from ethyl nitrite upon highly exothermic protonation by H 3 ϩ and CH 5 ϩ [21]. It was also demonstrated that the ion-dipole adduct is by far the most stable protomer and that the non planar Structure 2a, see Figure 1, represents the most stable conformer [12].…”

Section: Nitrosonium Complexes Of Water and Methanolmentioning

confidence: 99%

Nitrosation of thiols and thioethers in the gas phase: A combined theoretical and experimental study

Gerbaux

Wantier

Flammang

2004

J. Am. Soc. Mass Spectrom.

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Recent studies have demonstrated the biological importance of the interaction of nitric oxide with proteins such as cytochrome-c or hemoglobin. In particular, the possibility that the nitrosonium cation, NO ϩ , could reversibly bind to sulfide atom type was proposed. At pH values of biological relevance, nitrosation was proposed to occur through the action of NO ϩ carriers such as nitrosothiols or nitrosamines. In this context, the gas phase chemistry of protonated nitrosothiols is studied in the present work by a combination of mass spectrometry and computational methods. (J Am Soc Mass Spectrom 2004, 15, 344 -355)

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H2NO2+ ions in the gas phase: a mass spectrometric and post-SCF ab initio study

Cited by 33 publications

References 0 publications

Gas-phase NO ⁺ affinities

Gas-phase NO ⁺ affinities

Gas-phase nitronium ion affinities.

Nitrosation of thiols and thioethers in the gas phase: A combined theoretical and experimental study

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H2NO2+ ions in the gas phase: a mass spectrometric and post-SCF ab initio study

Cited by 33 publications

References 0 publications

Gas-phase NO + affinities

Gas-phase NO + affinities

Gas-phase nitronium ion affinities.

Nitrosation of thiols and thioethers in the gas phase: A combined theoretical and experimental study

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Product

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About

Gas-phase NO ⁺ affinities

Gas-phase NO ⁺ affinities