Selective ion-molecule reactions of lactams with dimethyl ether ions

The ion-molecule reactions of dimethyl ether ions CH₃OCH₃ ⁺ and (CH₃OCH₃)H⁺, and four- to seven-membered ring lactams with methyl substituents in various positions were characterized by using a quadrupole ion trap mass spectrometer and a triple-quadrupole mass spectrometer. In both instruments, the lactams were protonated by dimethyl ether ions and formed various combinations of [M + 13] ⁺, [M + 15] ⁺, and [M + 45] ⁺ adduct ions, as well as unusual [M + 3] ⁺ and [M + 16] ⁺ adduct ions. An additional [M + 47] ⁺ adduct ion was formed in the conventional chemical ionization source of the triple-quadrupole mass spectrometer. The product ions were isolated and collisionally activated in the quadrupole ion trap to understand formation pathways, structures, and characteristic dissociation pathways. Sequential activation experiments were performed to elucidate fragment ion structures and stepwise dissociation sequences. Protonated lactams dissociate by loss of water, ammonia, or methylamine; ammonia and carbon monoxide; and water and ammonia or methylamine. The [M + 16] ⁺ products, which are identified as protonated lactone structures, are only formed by those lactams that do not have an N-methyl substituent. The ion-molecule reactions of dimethyl ether ions with lactams were compared with those of analogous amides and lactones.     

Ion-molecule reactions of dimethyl ether cations with polycyclic aromatic hydrocarbons in a quadrupole ion trap mass spectrometer

The reaction chemistry between dimethyl ether (DME) cations and polycyclic aromatic hydrocarbons (PAHs) was elucidated by isolating three different types of DME ions using a quadrupole ion trap and reacting them individually with neutral PAH molecules eluting from a gas chromatographic column. The results obtained show that the CH(2)OCH(3)(+) ion (m/z 45) reacts via adduct formation followed by elimination of CH(3)OH, the (CH(3))(2)OH(+) (m/z 47) ion serves as proton donor and the (CH(3))(3)O(+) ion (m/z 61) does not yield any reaction products. Copyright 1999 John Wiley & Sons, Ltd.     

Ion-molecule reactions of cyclopentadienyl- tricarbonylmanganese derivatives with 18-crown-6 in the gas phase

The ion-molecule reactions of 18-crown-6 (L) with ions produced from cymantrene and its derivatives under electron impact are studied. It is shown that RXC₅H₄MnL⁺ ions (RX = the substituent in the cyclopentadienyl ring) can be produced by two reaction pathways: (i) by the addition of RXC₅H₄Mn⁺ to crown ether; and (ii) by the exchange of carbonyl ligands in RXC₅H₄MnCO)_x⁺ ions (x = 1-2) for the macrocyclic molecule. The formation of RMnL⁺ ions, where R = H, Me, Ph, OH, NMe₂, proceeds via the substitution of C₅H₄X in the isomerized form of the decarbonylated ions (RMn⁺C₅H₄X) for L. The relative abundances of the RXC₅H₄MnL⁺ and RMnL⁺ ions provide information about the structure of the RXC₅H₄Mn⁺ ions. The probability of synthesizing stable “sandwich” species of the C₅H₄Mn⁺ type in the condensed phase is predicted.     

Elimination reactions of ions in the gas phase

The loss of water from the molecular ion of 2-adamantanol was investigated using specifically labelled deuterium derivatives, and, in particular that stereospecifically labelled in position 4. Water is lost predominantly in a stereospecific 1, 3 fashion by two clearly distinguishable mechanisms. Determination of metastable ion characteristics proved to be essential for drawing this distinction.     

An investigation of site-selective gas-phase reactions of amino alcohols with dimethyl ether ions

The reactions of dimethyl ether ions with neutral amino alcohols were examined in both a quadrupole ion trap mass spectrometer and a triple quadrupole mass spectrometer. These ion-molecule reactions produced two types of ions: the protonated species [M+l]⁺ and a more complex product at [M+13]⁺. The abundance of the [M+13]⁺ ions relative to that of the [M+1]⁺ ions decreases with increasing formal interfunctional distance. Multistage collision-activated dissociation techniques were used to characterize the [M+13]⁺ product ions, their reactivities, and the mechanisms for their formation and dissociation. In addition, molecular semiempirical calculation methods were used to probe the thermochemistry of these reactions. Reaction at the amino alcohol nitrogen site is favored, and the resulting [M+13]⁺ addition products may cyclize for additional stabilization. Comparisons were made among the behavior of related compounds, such as alcohols, diols, amines, and diamines. The alcohols reacted only to form the protonated species, but the diols, amines, and diamines all formed significant amounts of [M+13]⁺ ions or related dissociation products.     

Kinetics of the reactions of the hydroxyl radical with dimethyl ether and diethyl ether

Absolute rate coefficients for the reactions of the hydroxyl radical with dimethyl ether (k₁) and diethyl ether (k₂) were measured over the temperature range 295–442 K. The rate coefficient data, in the units cm³ molecule^?1 s^?1, were fitted to the Arrhenius equations k₁ (T) = (1.04 ± 0.10) × 10^?11 exp[?(739 ± 67 cal mol^?1)/RT] and k₂(T) = (9.13 ± 0.35) × 10^?12 exp[+(228 ± 27 kcal mol^?1)/RT], respectively, in which the stated error limits are 2σ values. Our results are compared with those of previous studies of hydrogen-atom abstraction from saturated hydrocarbons by OH. Correlations between measured reaction-rate coefficients and C? H bond-dissociation energies are discussed.     

Ion-molecule reactions of several ions with ethylene oxide and propenal in a selected ion flow tube

The selected ion flow tube (SIFT) technique has been used to investigate the ion-molecule reactions of several ions with the neutral molecules ethylene oxide, CH(2)OCH(2)-c, and propenal, CH(2)CHCHO. Both molecules have been identified in hot-core star forming regions [] and have significance to astrochemical models of the interstellar (ISM) and circumstellar medium (CSM). Moreover, the molecules contain functional groups, such as the epoxide group (ethylene oxide) and an aldehyde group, which are part of a conjugated pi-electron system (propenal) whose reactivities have not been studied in detail in gas-phase ion-molecule reactions. The larger recombination energy ions, Ar(+) and N(2)(+), were reacted with the neutrals to give insight into general fragmentation tendencies. These reactions proceeded via dissociative charge-transfer yielding major fragmentation products of CH(3)(+) and HCO(+) for ethylene oxide and CH(2)CH(+) and HCO(+) for propenal. The amino acids glycine and alanine are of particular interest to astrobiology, especially if they can be synthesized in the gas phase. In an attempt to synthesize amino acid precursors, ethylene oxide and propenal were reacted with NH(n)(+) (n = 1-4) and HCNH(+). As might be expected from the proton detachment energies, NH(+), NH(2)(+), and HCNH(+) reacted via proton transfer. NH(3)(+) reacted with each molecule via H-atom abstraction to produce NH(4)(+), and NH(4)(+) reacted via a ternary association. All binary reactions proceeded near the gas kinetic rate. Several associated molecule switching reactions were performed and implications of these reactions to the structures of the association products are discussed Ikeda et al. and Hollis et al.     

Ion-molecule reaction of alkanenitriles and transition-metal ions in the gas phase: A study on fragmentation mechanism of the adducts

Gas-phase ion-molecule reactions between transition-metal ions (Mn +, Fe+, Co+, Ni +) and propionitri1e and acetonitrile were investigated. Ion-molecule adducts were prepared in a modified fast atom bombardment source and their metastable and collision-induced fragmentations, occurring in the frrst held-free region of an E/B configuration instrument, were studied by means of B/E linked scans. The experimental data suggest a coexistence of both “end-on” and “side-on” coordination modes; the former undergoes ligand detachment alone, whereas the latter loses methyl and ethyl radicals by insertion of M+ into organic substrates and further produces ethylene via a l3-hydrogen transfer. An order for the bonding energy of RCN-M+ is also suggested: RCN-Ni+> RCN-Co+> RCN-Fe+> RCNMn+.     

Ion-molecule reactions in alkyl cyanides: Identification of reactive hydrogen in precursor ions

The relative abundance of [M + H]⁺ ions in the spectra of different nitriles depends on the nature of the nitrile. A new method for the identification of ion-molecule reactions has been applied, by determining the [M + D]⁺ ion intensity with respect to the [M + H]+ ion intensity in the spectra of partially deuteriated alkyl cyanides. This intensity ratio is correlated with the hydrogen-deuterium content of the suspected primary ions. In addition not only the reacting primary ions, but also the reactive hydrogen atom in the primary ion could be indicated. There is clear evidence that the proton attached to the nitrogen atom in the H₂C?C?N⁺˙? H rearrangement ion is transferred to the nitrile molecule.     

Heteronuclear diatomic transition-metal cluster ions in the gas phase: Reactivity and thermochemistry of AgFe+

The gas-phase chemistry of AgFe⁺ was studied by using Fourier transform ion cyclotron resonance mass spectrometry. AgFe⁺ is unreactive with alkanes but reacts with cyclic and linear (C4–C8) alkenes. The primary reactions are dominated by dehydrogenation and condensation. In addition, cluster splitting is observed in the reaction of AgFe⁺ with benzene. Secondary reactions generally involve cluster splitting with the loss of Ag, although AgFeC₅H ₆ ⁺ is observed to dehydrogenate cyclopentene to yield AgFeC₁₀H ₁₂ ⁺ . Ion-molecule reactions, collision-induced dissociation, and photodissociation experiments were used to determine the bond energiesD°(Fe⁺–Ag)=53±7 kcal/mol andD°(Ag⁺–Fe)=46±7 kcal/mol. These values in turn were used to calculateH _f (AgFe⁺)=296±7 kcal/mol andIP(AgFe)=6.5±0.3 eV. Related chemical and physical properties of CuFe⁺ are presented for comparison.     

Ion-molecule reactions in the gas phase. ix differentiation of enantiomeric menthols using a stereospecific sn2 process induced by a chiral reagent.

Stereospecific ion-molecule reactions of chiral reagents such as amino-alcohol with Mr,s,r and Ms,r,s enantiomeric alcohols (both menthols with R- and S-hydroxylic groups, respectively) yield both diastereomeric (Mr,r,s + AsH - H₂O)⁺ and (Ms,r,s + AsH - H₂O)⁺ ions. This specific gas phase synthesis combined with Mass Spectrometry/Mass Spectrometry analysis was applied to differentiate enantiomeric alcohols. Indeed,respective MIKE/CID spectra present differences in the daughter ion abundances which are useful for distinguishing between the initial alcohol configurations.     

Temperature dependence of the rate coefficients for the reactions of Br atoms with dimethyl ether and diethyl ether

The rate constants for the reactions of atomic bromine with dimethyl ether and diethyl ether were measured from approximately 300 to 350 K using the relative rate method. Both isooctane and isobutane were used as the reference reactants, and the rate constants for the reactions of these hydrocarbons were measured relative to each other over the same temperature range. The kinetic measurements were made by photolysis of dilute mixtures of bromine, the reference reactant, and the test reactant in mixtures of argon and oxygen at a total pressure of 1 atm. The resulting ratios of rate constants were combined with the absolute rate constant as a function of temperature for the reference reaction of Br with isobutane to calculate absolute rate constants for the reactions of Br with isooctane, dimethyl ether, and diethyl ether. The absolute rate constant, in the units cm3 molecule(-1) s(-1), for the reaction of Br with dimethyl ether was given by k = (3.8 +/- 2.4) x 10(-10) exp(-(3.54 +/- 0.21) x 10(3)/T) while for the reaction of Br with diethyl ether the rate constant is given by k = (2.8 +/- 2.7) x 10(-10) exp(-(2.44 +/- 0.32) x 10(3)/T). On the same basis, the rate constant for the reaction of Br with isooctane is given by k = (3.34 +/- 0.59) x 10(-12) exp(-(1.80 +/- 0.11) x 10(3)/T). In each case, the activation energy of the reaction is significantly smaller than the endothermicity of the reaction. This is discussed in terms of a complex mechanism for these reactions.     

Quantum-chemical interpretation of the difference in the field fragmentation of the molecular ions of dimethyl ether and dimethyl sulfide

The potential energy surfaces (PES) of the positive molecular ions of dimethyl ether and dimethyl sulfide were scanned by the LCAO-MO SCF method in the MINDO/3 valence approximation. On the PES of these radical-cations, apart from the minima corresponding to the equilbrium structures, each has a local minimum which belongs to a cyclic structure. The discovered differences in the stereochemical construction of the cyclic structures of the radical-cations (CH₃)₂O⁺'and (CH₃)₂S⁺' made it possible to explain features of the field fragmentation of their molecular ions. The effect of the external electric field of the ion source on the cyclization and fragmentation stages in the investigated radical-cations was traced.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 1, pp. 76–82, January–February, 1989.     

Evaluation of steric and substituent effects in phenols by competitive reactions of dimethyl ether ions in a quadrupole ion trap

Competitive reactions of dimethyl ether ions are used to probe the steric and substituent effects of substituted phenols and anisoles in a quadrupole ion trap. The relative percentages of protonation and methylene substitution from the reactions of dimethyl ether ions show a correlation with size, location, and number of subsrituents on the aromatic ring. Although gas-phase basicity measurements of the phenols show no discernible correlation with the percentages of competitive reactions, semiempirical calculations show a good correlation between the trend in heats of formation and the trend in methylene substitution percentage. Reactions with deuterated compounds show that the methylene substitution reaction occurs on the ring.     

Reactions of ions with molecules in the gas phase

Existing knowledge concerning the gas phase reactions of ions with molecules is summarized in terms of the identification of the reactions, the rate constants of the reactions, and the energetic properties of the ions observed to be formed and of those inferred as intermediates.     

Sulphonylium ions in the gas phase

Electron impact mass spectrometry was used to investigate the fragmentation of a series of arenesulphonyl chlorides. Sequential losses of a chlorine atom and sulphur dioxide from the molecular ions occurred and the reverse of these reactions had small critical energies that were generally unaffected by the ring substituent. However, an interesting intramolecular cyclization reaction occurring on the ortho-nitro derivative is discussed with the aid of kinetic energy release measurements on this derivative and on a model compound. Appearance energy measure ments combined with multiple scattering Xα calculations led to an estimate of the sulphur-chlorine bond strength in benzenesulphonyl chloride.     

Flowing afterglow studies of the reactions between negative ions and trimethylsilyl enol ethers. Regiospecific generation of gas phase enolate ions

Reactions of isomeric silyl enol ethers with fiuoride, amide or hydroxide ions in a flowing afterglow lead to the formation of relatively pure isomeric enolate anions. Isomeric enolates react specifically with neopentyl nitrite to give ionic products diagnostic of their structure.     

Ion–molecule reactions between organometallic ions and crown ethers in the gas phase

Ion–molecule reactions of the metal-containing ions LM⁺ (L = (acac)₂, acac, C₆H₆, C₅H₅; M = In, Ga, Co, Fe, Ni, Cr, Mn, Pd, Rh, Tl, La, Pr, Yb, Nd) with crown ethers in the gas phase were studied. Two major reactions were observed: adduct formation and substitution of a metal atom ligand by a crown ether. The relative abundances of the two reactions depends on the ease with which the metal atom may be reduced. Ligand substitution can involve hydrogen rearrangements with loss of acetylacetone or cyclopentadiene for crown ethers having mobile H atom(s). The use of ion–molecule reactions in the structural characterization of crown ethers and transition metalcontaining ions is discussed.     

Methylene substitution reactions in a quadrupole ion trap selectivity of ethylene,ethylene oxide,and dimethyl ether reactive ions

To elucidate the selectivity of methylene substitution reactions of monosubstituted and disubstituted oxyaromatic compounds in a low pressure quadrupole ion trap environment, the relative abundances of covalently bound and loosely bound adducts formed by ion/molecule reactions with ethylene (ET), ethylene oxide (ETOX), and dimethyl ether (DME) were compared. Adduct ions of all three reagent gases were formed in both a conventional ion source and a quadrupole ion trap and characterized by collisionally activated dissociation. For DME and ET, the covalently bound adducts formed at (M + 45)⁺ and (M + 41)⁺, respectively, are direct precursors to the methylene substitution product ions at (M + 13)⁺. ETOX and ET do not demonstrate the same functional group selectivity for methylene substitution as previously observed for DME. This is attributed to differences in reaction exothermicities and competing reactions.     

Gas-phase ion–molecule reactions in dilute mixtures of dimethyl ether in krypton. Bimolecular and clustering reactions

The results of high-pressure variable-temperature and variable ionizing electron energy studies of gas-phase ion-molecule reactions of dimethyl ether in krypton are presented. Near the ionization threshold a series of peaks corresponding to (CH₃OCH₃)_nH⁺ (n = 1-4) clusters are observed. At higher ionizing electron energies, two new series of peaks appear, corresponding to [CH₃OCH₂]⁺(CH₃OCH₃)_n and [(CH₃)₃O]⁺ (CH₃OCH₃)_n clusters. The onium ion, [(CH₃)₃O]⁺, has been previously reported at elevated temperatures under methane chemical ionization conditions. It was suggested that the onium ion is formed by reaction of (CH₃)₂OH⁺ with CH₃OCH₃ with subsequent elimination of methanel, i.e. by fragmentation of an adduct ion. The present results strongly suggest that, under our conditions, [CH₃OCH₂]⁺ rather than thermal (CH₃)₃OH⁺, is the precursor to [(CH₃)₃O]⁺.