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Gas-Phase Nitronium Ion Affinities F Proc. Natl. Acad. Sci. USA Vol. 92, pp. 8635-8639, September 1995 Chemistry Gas-phase nitronium ion affinities F. CACACE*t, G. DE PETRIStt, F. PEPI*, AND F. ANGELELLI* *Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive, Universita degli Studi di Roma "La Sapienza," Piazzale Aldo Moro, 5, 00185 Rome, Italy; and tDipartimento di Scienze Ambientali, Universita della Tuscia, v. S. C. De Lellis, 01100 Viterbo, Italy Communicated by Alfred P. Wolf, Brookhaven National Laboratory, Upton, NY, April 24, 1995 ABSTRACT Evaluation of nitronium ion-transfer equi- without further purification. The mass analyzed ion kinetic libria, L1NO' + L2 = L2NO' + L1 (where L1 and L2 are energy (MIKE) spectra were recorded using a ZAB-2F mass ligands 1 and 2, respectively) by Fourier-transform ion cyclo- spectrometer from VG Analytical (Manchester, U.K), whose tron resonance mass spectrometry and application of the chemical ionization source was fitted with a specially built device, kinetic method, based on the metastable fragmentation of designed to cool the source block, removing the heat radiated L1(NO+)L2 nitronium ion-bound dimers led to a scale of from the filament by a stream of cold N2. The spectra were relative gas-phase nitronium ion affinities. This scale, cali- recorded at temperatures ranging from 400 to 50°C, as measured brated to a recent literature value for the NO+ affinity of by a thermocouple inserted into the source block, using gaseous water, led for 18 ligands, including methanol, ammonia, mixtures of NO2 and the two ligands (L1 and L2), whose com- representative ketones, nitriles, and nitroalkanes, to absolute position was optimized to obtain the highest intensity of the NO+ affinities, that fit a reasonably linear general correlation L1(NO')L2 dimers, at total pressures in the 0.1- to 0.5-torr (1 torr when plotted vs. the corresponding proton affinities (PAs). = 133 Pa) range. Typical experimental conditions were as follows: The slope of the plot depends to a certain extent on the specific electron energy, 50 eV (1 eV = 1.602 x 10-19 J); repeller voltage, nature of the ligands and, hence, the correlations between the 0 V; emission current, 0.5 mA; accelerating voltage, 8 kV. Each NO+ affinities, and the PAs of a given class of compounds MIKE spectrum represents the average of at least 20 scans, with display a better linearity than the general correlation and may an energy resolution of 2000 full width at half-maximum (fwhm). afford a useful tool for predicting the NO+ affinity of a The equilibrium measurements were done by using a Bruker molecule based on its PA. The NO+ binding energies are (Billerica, MA) Spectrospin Apex TM 47e Fourier transform ion considerably lower than the corresponding PAs and well below cyclotron resonance mass spectrometer, equipped with an exter- the binding energies of related polyatomic cations, such as nal chemical ionization source and an XMASS TM Bruker data NO+, a trend consistent with the available theoretical results system. To prevent errors due to the different response of the on the structure and the stability of simple NO+ complexes. ionization manometer to different compounds, premixed gaseous The present study reports an example of extension of the mixtures, obtained by weighted amounts of the reactants, were kinetic method to dimers, such as L1(NO+)L2, bound by used. polyatomic ions, which may considerably widen its scope. Finally, measurement of the NO' affinity of ammonia allowed evaluation ofthe otherwise inaccessible PA ofthe amino group RESULTS of nitramide and, hence, direct experimental verification of Fourier Transform Ion Cyclotron Resonance Equilibrium previous theoretical estimates. Measurements. Evaluation of ligand exchange equilibria, The study of the complexes formed in the gas phase by NO2 L,NO+ + L2 = L2NO2 + Ll, [1] is currently the focus of considerable fundamental interest free (1-11) and, in addition, has a direct bearing on areas ranging allows direct determination of the corresponding energy from mechanistic organic chemistry (12-19) to atmospheric change, AG', provided that the equilibrium constant can be accurately measured, which requires attainment of true equi- chemistry, clustering and nucleation phenomena, intracluster librium, unperturbed by significant side reactions. In the reactivity (20-30), etc. In view of the considerable interest of is the problem and of the scant experimental information cur- specific application, CH3O(NO2)2, the nitrating reagent, rently available (31-33), we have undertaken a systematic prepared in the external chemical ionization source of a study of the binding energy (BE) of NO+ to representative Fourier transform ion cyclotron resonance mass spectrometer ligands, aimed at the construction of a gas-phase nitronium and driven into the resonance cell, where it nitrates both ion-affinity scale. ligands, present in a known concentration ratio. One of the To this end, we have applied the Fourier-transform ion nitrated complexes is isolated by selective-ejection techniques cyclotron resonance mass spectroscopy equilibrium method and allowed to equilibrate in the mixture of the ligands. largely used in proton affinity (PA) measurements (34) to Application of the method is prevented in many cases by NO' transfer reactions and extended the kinetic method, so incursion of fast proton-transfer reactions that perturb the far used exclusively in PA and gas-phase acidity determina- equilibrium-e.g., the nitronium ion transfer, tions (35, 36), to nitronium ion-bound dimers. [C2H5OH-NO2]+ + NH3 MATERIALS AND METHODS = [H3N-NO2]+ + C2H5OH, [la] All chemicals were obtained as research-grade products from undergoes competition by proton transfer to ammonia from Aldrich and were used without further purification. The gases both nitrated complexes, which react as the conjugate acids of were purchased from Matheson with a stated purity >99.95 mol ethyl nitrate and of nitramide. Furthermore, in the case of %, except NO2, for which purity was >99.5 mol %, and were used ligands of low ionization potential the study of equilibrium 1 The publication costs of this article were defrayed in part by page charge Abbreviations: PA, proton affinity; BE, binding energy; RP, reference payment. This article must therefore be hereby marked "advertisement" in pair; MIKE, mass analyzed ion kinetic energy. accordance with 18 U.S.C. §1734 solely to indicate this fact. tTo whom reprint requests should be addressed. 8635 Downloaded by guest on September 24, 2021 8636 Chemistry: Cacace et aL Proc. Natl. Acad. Sci. USA 92 (1995) is adversely affected by competing charge-transfer reactions. Table 1. AG' changes from the equilibrium and the As a consequence, application of the equilibrium method is kinetic method restricted to those systems where proton- and/or electron- -AG3OO, kcal.mol-l* transfer processes are sufficiently slower than reaction 1, as in the example illustrated in Fig. 1. In most cases, equilibrium 1 Equilibrium Kinetic could be attained from both sides, and the AG' changes L2 method method reported in Table 1 are the mean values of sets of at least three H20 CH30H 1.9t RP* measurements, performed at different [L1]/[L2] ratios, char- H20 CH2(CN)2 2.1 acterized by SDs appreciably lower than the ±0.1 kcal mol-1 CH30H CH3NO2 1.3 (1 cal = 4.184 J) uncertainty quoted, which reflects instead a CH3NO2 C2H5NO2 1.4 1.1 conservative estimate of the errors affecting the [L1]/[L2] C2H5NO2 CH3CN 1.6 1.3 ratio, the measurement of the ionic intensities, etc. CH3CN CH3COCH3 0.5 0.6 The Kinetic Method. The limitations of the equilibrium C2H5NO2 CH3COCH3 1.9 1.8 method have suggested extension to nitronium ion-bound CH3COCH3 C2H5CN 0.5 0.6 dimers of the kinetic method developed by Cooks and co- CH3CN C2H5CN 0.9 1.2 workers (35, 36) for proton-bound dimers and subsequently CH3COCH3 CH3COC2H5 0.8 RP applied to alkali cation-bound dimers (37) and other metal C2H5CN CH3COC2H5 0.5 cation-bound clusters (38-41). It is a limiting procedure, based CH3COC2H5 i-C3H7CN 0.2 on several nonrigorous assumptions that nevertheless has C2H5CN i-C3H7CN 0.7 RP proved highly successful in a var-iety of applications, especially CH3COCH3 i-C3H7CN 1.2 RP in those systems where weakly bound dimers undergo simple CH3CN i-C3H7CN 1.5 RP dissociation kinetics, which is the case of many nitronium i-C3H7CN (C2H5)20 0.2 RP ion-bound dimers (see below). C2H5CN (C2H5)20 0.5 0.8 In the case of interest, application of the kinetic method is CH3COCH3 (C2H5)20 1.1 based on the MIKE spectrometry of LI(NO')L2 nitronium CH3CN (C2H5)20 1.4 ion-bound dimers, obtained by N02/chemical ionization of (C2H5)20 NH3 0.2 gaseous mixtures of the ligands. The conceivable formation of i-C3H7CN NH3 0.2 clusters-e.g., proton-bound dimers of the same m/z ratio but CH3COCH3 NH3 1.0 structurally different from nitronium ion-bound dimers-has i-C3H7CN C6H5CN 0.5 0.4 required preliminary selection of the species suitable for CH3COC2H5 C6H5CN 0.6 application of the kinetic method. Fortunately a systematic C6H5CN (C2H5)2CO 0.1 survey has allowed identification of many (Li, L2, NO2)+ (C2H5)20 (C2H5)2CO 0.5 clusters whose metastable fragmentation occurs exclusively via i-C3H7CN (C2H5)2CO 0.4 the competing processes CH3COC2H5 (C2H5)2CO 0.8 0.5 (C2H5)2CO t-C4HqCOCH3 0.3 t-C4HqCOCH3 (i-C3H7)2CO 0.8 k[ (C2H5)2CO (i-C3H7)2CO 1.1 L1(NO+)L2 CH3COC2H5 (i-C3H7)2CO 1.8 (i-C3H7)2CO C6H5COCH3 0.3 k3 L1NO+ +L2, [3] t-C4HqCOCH3 C6H5COCH3 0.8 (C2H5)2CO C6H5COCH3 1.3 suggesting that the dissociating species has the structure of a C6H5COCH3 (C6H5)2CO 0.8 L1(NO+)L2 nitronium ion-bound dimer, as in the representa- L, ligand; i-C3H7, isopropyl; t-C4H9, tert-butyl.
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