Rearrangements and fragmentations of [C2H5S]+ ions

[C₂H₅S]⁺ ions (m/e 61) with different initial structures were generated in the mass spectrometer from twelve precursor ions. Abundance ratios of competing metastable ion decompositions were used to determine whether these ions decompose through the same or different reaction channels. It was concluded that all [C₂H₅S]⁺ ions isomerize to a common structure or mixture of structures prior to decomposition in the first field free region. From ¹³C labelling experiments it was concluded that [C₂H₅S]⁺ ions generated from the molecular ions of 2-propanethiol-2-[¹³C], partially rearrange to a symmetrical structure before decomposition to [CHS]⁺ and CH₄, whereas in [C₂H₅S]⁺ ions generated from the the molecular ions of 1,2-bis-(thiomethoxy-[¹³C]) ethane, the two carbon atoms become fully equivalent before CH₄ loss occurs.     

Doubly charged ion mass spectra: IV—chlorinated and brominated alkanes

Doubly charged ion mass spectra have been obtained for 42 chlorinated and brominated n-alkane (methyl through octyl) hydrocarbons. A double focusing Hitachi RMU-7L mass spectrometer, operated at 1.6kV accelerating voltage, has been used to measure the spectra. Molecular doubly charged ions have not been observed. Intense fragment ions have been produced from extensive H and halogen loss as well as C? C bond rupture of the parent molecule. The most abundant ions in the doubly charged ion spectra observed in this investigation resulted from reactions of [Cl]²⁺˙, [Br]²⁺˙, [CCL₂]²⁺, [C₂H₂Cl]²⁺˙, [C₃H₂]²⁺, [C₃HCl]²⁺, [C₃HBr]²⁺, [C₄H₃]²⁺˙, [C₄H₄]²⁺, [C₄H₆Br]²⁺˙, [C₄H₈Br]²⁺˙, [C₅H₂]²⁺, [C₆H₆]²⁺, [C₆H₈]²⁺ and [C₇H₈]²⁺. The prominent doubly charged fragment ions formed by electron impact of the smaller halogenated alkanes generally contained halogen, whereas ions of the type [C_nH_x]²⁺ were dominant in the spectra of higher molecular weight mono- and dihalogenated alkanes. Appearance energies of several ions have been measured. A geometry optimized quantum mechanical SCF treatment has been used to compute energies, charge densities and structures of doubly charged halogenated alkane ions.     

Doubly charged ion mass spectra: III—N-alkanes

Doubly charged ion mass spectra have been obtained for 15 n-alkane hydrocarbons. Spectra were measured using a Nier-Johnson geometry Hitachi RMU-7L mass spectrometer operated at 1.6kV accelerating voltage. Fragment ions, which resulted from C? C bond rupture and extensive H loss, dominated the spectra. Molecular ions have not been observed. The most intense ions in the doubly charged ion mass spectra of n-alkanes were [C₂H₄]²⁺, [C₃H₂]²⁺, [C₄H₃]²⁺, [C₅H₂]²⁺, [C₆H₆]²⁺, [C₆H₈]²⁺, [C₇H₆]²⁺, [C₇H₈]²⁺, [C₈H₆]²⁺ and [C₈H₈]²⁺. Appearance energies for forming the prominent doubly charged fragment ions have been measured and range from 27.5 eV to energies greater than 60eV. A geometry optimized SCF approach has been used to compute the energies and structures of prominent ions in the doubly charged mass spectra.     

A study of [C7H8]+˙ and [C7H8]2+ ions formed from different precursor molecules

On the basis of unimolecular and collisionally activated decompositions, as well as their charge stripping behaviour, [C₇H₈]⁺˙ and [C₇H₈]²⁺ ions from a variety of precursors have been studied. In particular, structural characteristics of molecular ions of toluene, cycloheptatriene, norborna-2,5-diene and quadricyclane have been compared to those of [C₇H₈]⁺˙ and [C₇H₈]²⁺ rearrangement fragment ions obtained from n-butylbenzene, 2-phenylethanol and n-pentylbenzene. Severe interferences from [C₇H₇]^2+˙ ion fragmentations have been observed and rationalized.     

Multiple ionization,charge separation and charge stripping reactions involving polycyclic aromatic compounds

The 70 eV electron ionization mass spectra of polycyclic aromatic compounds are characterized by the presence of relatively stable multiply charged molecular ions [M]ⁿ⁺ (n=2–4). When generated from the compounds benzene, napthalene, anthracene, phenanthrene, 2,3-benzanthracene, 1,2-benzanthracene, chrysene, 9,10-benzophenanthrene and pyrene, the relative abundances of the multiply charged ions increase dramatically with the number of rings. These compounds form multiply charged molecular ions (n=2, 3) which undergo unimolecular decompositions indicative of considerable ionic rearrangement. The main charge separation processes observed here [M]²⁺→m₁⁺+m₂⁺, [M]³⁺˙→m₃⁺+m→+m₄²⁺) involve, in almost every case, one or more of the products [CH₃]⁺, [C₂H₃]⁺˙ and [C₃H₃]⁺. This suggests the existence of preferred structures amongst the metastable parent ions. Information on the relative importance of the various fragmentation pathways is presented here along with translational energy release data. Some tentative structural information about the metastable ions has been inferred from the translational energy release on the assumption that the released energy is due primarily to coulombic repulsion within the transition state structure. For the triply charged ions these interpretations have necessitated the use of a coulombic repulsion model which takes account of an extra charge. Vertical ionization energies for the process [M]ⁿ⁺+G→[M](ⁿ⁺¹)+G+e^? (charge stripping) have also been determined where possible for n=1 and 2 and the results from these experiments allow the derivation of simple empirical equations which relate successive ionization energies for the formation of [M]²⁺ and [M]³⁺˙ to the appearance energy of [M]⁺˙.     

Metastable ion studies. IV—thermochemistry and ion structures among fragmenting [C3H6]+· ions

Metastable ion peak shapes, dimensions and relative abundances have been measured for the three fragmentations [C₃H₆]⁺· → [C₃H₄]⁺· + H₂, [C₃H₆]⁺· → [C₃H₅]⁺ + H· and [C₃H₆]⁺· → [C₃H₃]⁺ + H₂ + H·. [C₃H₆]⁺· ions were derived from propene, cyclopropane, tetrahydrofuran, cyclohexanone, 2-methyl but-1-ene and cis-pent-2-ene. Activation energies for these fragmentations have been evaluated. Three daughter ion dissociations ([C₃H₅]⁺ → [C₃H₃]⁺ + H₂, [C₃H₅]⁺ → [C₃H₄]⁺· + H· and [C₃H₄]⁺· → [C₃H₃]⁺ + H·) have been similarly examined. Ion structures have been determined and the metastable energy releases have been correlated with the thermochemical data. It is concluded that the molecular ions of propene and cyclopropane become structurally indistinguishable prior to fragmentation and that differences in their metastable ion characteristics can be ascribed wholly to internal energy differences; the latter can be correlated with the photoelectron spectra of the isomers. The pathway for the consecutive fragmentation which generates the metastable ion peak (m/e 42 → m/e.39) has been shown to be It is likewise concluded that fragmentating [C₃H₆]⁺· ions generated from the various precursor molecules are also structurally indistinguishable and cannot be classified with either molecular ion of the isomeric C₃H₆ hydrocarbons.     

Structure and formation of gaseous [C4H5O]+ Ions. II–Ions of the type HCC?\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}(OH)(CH3)

Loss of an alkyl group X? from acetylenic alcohols HC?C? CX(OH)(CH₃) and gas phase protonation of HC?C? CO? CH₃ are both shown to yield stable HC?C? \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}(OH)(CH₃) ions. Ions of this structure are unique among all other [C₄H₅O]⁺ isomers by having m/z 43 [C₂H₃O]⁺ as base peak in both the metastable ion and collisional activation spectra. It is concluded that the composite metastable peak for formation of m/z 43 corresponds to two distinct reaction profiles which lead to the same product ion, CH₃\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}?O, and neutral, HC?CH. It is further shown that the [C₄H₅O]⁺ ions from related alcohols (like HC?C? CH(OH)(CH₃)) which have an α-H atom available for isomerization into energy rich allenyl type molecular ions, consist of a second stable structure, H₂C?\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}? C(OH)?CH₂.     

Low-energy,low-temperature mass spectra. 10—urethanes

The 12.1 eV, 75°C electron impact mass spectra of 24 urethanes, RNHCO₂C₂H₅ [R ? H, C₂H_{2n +1} (n = 1-8), CH₂?CHCH₂, Ph, PhCH₂ and PhCH₂CH₂], and seven symmetrically disubstituted urethanes R₂NCO₂C₂H₅ (R ? C_n H_{2n + 1} (n = 1?4)) are reported and discussed. All 31 spectra show appreciable molecular ion peaks. For n ?Cn H_{2n +1} NHCO₂C₂H₅, M^{+ ˙} usually is the most abundant ion in the spectrum. A peak at m/z 102 of comparable intensity also is present; this corresponds to formal cleavage of the bond connecting the α- and β-carbon atoms in the N-alkyl group, though it is unlikely that the daughter ion has the structure [CH₂?NHCO₂C₂H₅]⁺. In the RNHCO₂C₂H₅ series, branching at the α-carbon atom enhances the relative abundance of the ion arising by notional α-cleavage at the expense of that of M^{+ ˙}. Formal cleavage of the bond between β- and γ-carbon atoms occurs to some extent for [RNHCO₂C₂H₅]⁺˙ ions; this reaction provides information on the degree of branching at the β-carbon, especially if metastable molecular ions are considered. The higher n-C_nH_{2n +1}NHCO₂C₂H₅ (n = 5?8) urethanes exhibit two other significant ions in their mass spectra. First, there is a peak at [M ? C₂H₅]⁺. Secondly, a peak is present at m/z 90; the most plausible structure for this ion is [H₂N(HO)COC₂H₅]⁺, arising by double hydrogen transfer from the alkyl group and expulsion of a [C_nH_{2n ?1}]˙ radical. Ions originating from secondary decomposition of the primary ionic species are generally of only very low abundance in these spectra.     

An investigation of the decomposition of the intermediate ions produced by electron-impact. II—[C7H7]+ ions from several halogenotoluenes

The structure and decomposition of the [C₇H₇]⁺ ions produced by electron-impact from o-, m- and p-chlorotoluene, o-, m- and p-bromotoluence, and p-iodotoluence, have been investigated. By determining the relative abundance of normal and metastable ions, these [C₇H₇]⁺ ions at electron energy of 20 eV are shown to be so-called ‘tropylium ions’. The amount of the internal energy of the [C₇H₇]⁺ ion estimated by the relative ion abundance ratios, ? [C₅H₅]⁺/[C₇H₇]⁺ and m*/[C₇H₇]⁺ for the decomposition \documentclass{article}\pagestyle{empty}\begin{document}$ [{\rm C}_{\rm 7} {\rm H}_{\rm 7}]^ + \mathop \to \limits^{m^* } [{\rm C}_{\rm 5} {\rm H}_{\rm 5}]^ + + {\rm C}_{\rm 2} {\rm H}_{\rm 2} $\end{document}, is in the order iodotoluene > bromotoluene > chlorotoluene. The heats of formation of the activated complexes for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$ [{\rm C}_{\rm 7} {\rm H}_{\rm 7}]^ + \mathop \to \limits^{m^* } [{\rm C}_{\rm 5} {\rm H}_{\rm 5}]^ + + {\rm C}_{\rm 2} {\rm H}_{\rm 2} $\end{document} were estimated. The values suggest that the decomposing [C₇H₇]⁺ ions from various halogenotoluenes are identical in structure.     

Positive chemical ionization triple‐quadrupole mass spectrometry and ab initio computational studies of the multi‐pathway fragmentation of phthalates

We report the first positive chemical ionization (PCI) fragmentation mechanisms of phthalates using triple‐quadrupole mass spectrometry and ab initio computational studies using density functional theories (DFT). Methane PCI spectra showed abundant [M + H]⁺, together with [M + C₂H₅]⁺ and [M + C₃H₅]⁺. Fragmentation of [M + H]⁺, [M + C₂H₅]⁺ and [M + C₃H₅]⁺ involved characteristic ions at m/z 149, 177 and 189, assigned as protonated phthalic anhydride and an adduct of phthalic anhydride with C₂H₅⁺ and C₃H₅⁺, respectively. Fragmentation of these ions provided more structural information from the PCI spectra. A multi‐pathway fragmentation was proposed for these ions leading to the protonated phthalic anhydride. DFT methods were used to calculate relative free energies and to determine structures of intermediate ions for these pathways. The first step of the fragmentation of [M + C₂H₅]⁺ and [M + C₃H₅]⁺ is the elimination of [R? H] from an ester group. The second ester group undergoes either a McLafferty rearrangement route or a neutral loss elimination of ROH. DFT calculations (B3LYP, B3PW91 and BPW91) using 6‐311G(d,p) basis sets showed that McLafferty rearrangement of dibutyl, di(‐n‐octyl) and di(2‐ethyl‐n‐hexyl) phthalates is an energetically more favorable pathway than loss of an alcohol moiety. Prominent ions in these pathways were confirmed with deuterium labeled phthalates. Copyright © 2010 John Wiley & Sons, Ltd.     

Metastable ion studies. III—composite metastable peaks in fragmentations of some small hydrocarbon cations

Composite metastable peaks are generated in the unimolecular fragmentations (i) [C₃H₅]⁺ → [C₃H₃]⁺ + H₂ (flat-top upon flat-top) and (ii) [C₄H₉]⁺ → [C₃H₅]⁺ + CH₄ (flat-top and gaussian). The measurement of appearance potentials and kinetic energy releases lead us to conclude, in agreement with earlier proposals, that in (i) the components can arise from the generation of the isomeric cyclopropenium and propargyl daughter cations. In (ii) the components are proposed to arise from the fragmentation of tert- and sec-butyl cations yielding allyl as the common daughter ion. The composite peak observed in the fragmentation (iii) [C₃H₄]⁺· → [C₃H₃]⁺ + H· is shown to be present only if the decomposing molecular ion is large enough to also produce [C₆H₈]²⁺ ions. The second component in (iii) then arises from the reaction [C₆H₈]²⁺ → [C₆H₆]²⁺ + H₂.     

Adduct ion formation by metal complexes under methane negative chemical ionization conditions

Negative chemical ionization mass spectrometry is used as a probe to examine reactions between hydrocarbon radicals and metal complexes in the gas phase. The methane negative chemical ionization mass spectra of 27 complexes of cobalt(II ), nickel(II ) and copper(II ) in the presence of O₄, O₂N₂ and N₄ donor atom sets are characterized by two dominant series of adduct ions of the form [M + C_nH_2n]^? and [M + C_nH_2n+1]^? at m/z values above the molecular ion, [M]^?. Insertion of the CH radical into the ligand followed by radical/radical recombination and electron capture is proposed as the major mechanism leading to the formation of [M + C_nH_2n]^? adduct ions. A second pathway involves ligand substitution by C_nH_2n+1 radicals concomitant with H elimination and electron capture. Oxidative addition at the metal followed by ionization is suggested as the principal pathway for the formation of [M + C_nH_2n+1]^? adduct ions.     

Substituent effects in the mass spectra of diethyl phenyl phosphates

The mass spectra of diethyl phenyl phosphates show substituent effects with electron-donating groups favouring the molecular ion M⁺˙, and the [M? C₂H₄]⁺˙, [M – 2C₂H₄]⁺˙ and [XPhOH]⁺˙ ions. The [PO₃C₂H₆]⁺ (m/z 109) and [PO₃H₂]⁺ (m/z 81) ions are favoured by electron-withdrawing groups. Results suggest that the formation of the [XPhC₂H₃]⁺˙ ion involves rearrangement of C₂H₃ to the position ortho to the phosphate group. Ortho effects are also observed.     

On the unimolecular loss of acetylene from metastable C11H9]+ ions

Extensive ¹³C labelling experiments demonstrate that loss of acetylene from metastable [C₁₁H₉]⁺ ions is a complex process, which can be described quantitatively in terms of a four-parameter model. The major reaction path (77.8%) involves scrambling of all 11 carbon atoms. Insight into the reaction details is provided neither by the kinetic energy release associated with the reaction [C₁₁H₉]⁺ → [C₉H₇]⁺ + C₂H₂ nor by the analysis of the collisional activation mass spectra of the resulting [C₉H₇]⁺ ions.     

Benzyl vs. tropylium ions in the decomposition of some alkylnitrobenzenes

The [NO₂C₇H₆]⁺ ions generated from m-alkylnitrobenzenes have been shown to be different in their decomposition from those generated from p-alkylnitrobenzenes, even when the alkyl group is methyl and the departing fragment a hydrogen radical. Thus, in these cases even molecular ions of relatively high internal energy do not reversibly ring-expand to cycloheptatriene structures. In addition, the [NO₂C₇H₆]⁺ ions, assumed to be benzylic, do not ring-expand to nitrotropylium ions at internal energies sufficient to cause subsequent loss of NO or NO₂ from the p- and m-isomers, respectively.     

Density functional theory and RRKM calculations of the gas‐phase unimolecular rearrangements of methylfuran and pyran ions before fragmentations

The potential energy profiles for the mutual conversion of the isomeric molecular ions [C₅H₆O]^+? of 2‐methylfuran, 3‐methylfuran and 4H‐pyran and the fragmentations that lead to [C₅H₅O]⁺ ions were obtained from calculations at the B3LYP/6‐311G + + (3df,3pd)//B3LYP/6‐31G(d,p) level of theory. The various competing unimolecular processes were characterized by their RRKM microcanonical rate coefficients, k(E), using the sets of reactant and transition state frequencies and the kinetic barriers obtained from the density functional method. In either a high‐ or a low‐energy regime, the pyrylium ion [C₅H₅O]⁺ is generated directly from the 4H‐pyran molecular ion by a simple cleavage. In contrast, in the metastable kinetic window, the molecular ions of methylfurans irreversibly isomerize to a mixture of interconverting structures before dissociation, which includes the 2H‐ and 3H‐pyran ions. The hydrogen atoms attached to saturated carbons of the pyran rings are very stabilizing at the position 2, but they are very labile at position 3 and can be shifted to adjacent positions. Once 4H‐pyran ion has been formed, the C? H bond cleavage begins before any hydrogen shift occurs. According to our calculation, there would not be complete H scrambling preceding the dissociation of the molecular ions [C₅H₆O]^+?. On the other hand, as the internal energy of the 2‐methylfuran molecular ion increases, H^? loss can become more important. These results agree with the available experimental data. Copyright © 2009 John Wiley & Sons, Ltd.     

Field ionization mass spectrometry—IV. Isotopically labeled heptanals

The field ionization (FI) mass spectra of n-heptanal and a series of deuterium labeled analogs have been studied, with the objectives of initiating systematic investigations of reaction mechanisms of FI produced ions and to permit comprison with those found for other ionization processes. It is now recognized that FI ions have: (a) lower average internal energies and (b) shorter residence times than similar ions generated by electron-impact (EI), and the possibility exists of H/D-randomization occuring in ions formed by desorption from the emitter, by unimolecular decomposition close to the emitter and by either ‘fast’ or ‘slow’ metastable decompositions. In this study only the peak shifts of normal ions could be utilized; accurate mass measurements of all major ions revealed elemental compositions similar to EI. A site-specific McLafferty rearrangement gave the base peak at m/e 44 ([C₂H₄O]^+.), although the apparently complementary ion at m/e 70 ([C₅H₁₀]^+.) arose in a less specific process. Ions at m/e 43 ([C₃H₇]⁺) and 71 ([C₅H₁₁]⁺ 80%; [C₄H₇O]⁺ 20%) were apparantly generated without significant H/D-scrambling. Of special interest was the observation of the rearrangement ion at m/e 86 ([C₅H₁₀O]^+.) caused by loss of C-2 and C-3 as C₂H₄, as found for EI. It is concluded that at least in this system, decomposing molecular ions formed: (a) in the gas phase extremely close to the emitter and/or (b) on the emitter surface, have lifetimes sufficiently short to preclude complete H/D randomization. The results also provide evidence for common fragmentation mechanisms for heptanal molecular ions at both the low end and the high end of the energy distribution.     

[C]+· and [CH]+ from doubly charged ions formed from malononitrile

The metastable ions [M]²⁺, [M – H]²⁺· and [M – H₂]²⁺ from malononitrile fragment by loss of [CH]⁺, [C]⁺· and [C]⁺·, respectively. The reaction of the molecular ion involves the methylene and nitrile carbon atoms in the statistical probability ratio, while that of [M – H]²⁺· involves exclusively the nitrile carbon and that of [M ? H₂]²⁺ involves an approximately equal contribution, from both sources. It is suggested that the metastable molecular ion fragments through a bipyrimidal intermediate.     

Isomerisation of hydrocarbon ions:I—Isomeric octanes: Acollisional actiation study

The molecular ions of isomeric octanes retain their structural identity, while their alkyl fragments [C_nH_2n+1]⁺ (n = 3 to 7) isomerise to common structures prior to decomposition. Structures for [C₆H₁₃]⁺ and [C₇H₁₅]⁺ ions are proposed.     

Comparison of [C6H6]2+ ion structures: Application of electron capture induced decomposition to the study of isomers

Structures of [C₆H₆]²⁺ ions formed by electron impact from benzene, 2,4-hexadiyne and 1,5-hexadiyne have been investigated by the recently developed electron capture induced decomposition method, by charge-separation reactions and by ion abundances in electron impact mass spectra. Significant differences were found among the isomers indicating the structural integrity of these [C₆H₆]²⁺ ions. The observed differences indicate that the most likely atomic configuration of [C₆H₆]²⁺ ions produced from benzene and 2,4-hexadiyne is the same as in the corresponding neutral species. A new method is suggested by which the structure (atomic configuration) of doubly charged ions may be determined.