Loss Of HCN Research Articles

Intramolecular electrophilic aromatic substitution in gas-phase fragmentation of protonated N-benzylbenzaldimines.

In this study, the gas-phase fragmentations of protonated N-benzylbenzaldimines were investigated by electrospray ionization tandem mass spectrometry (ESI-MS(n)). Upon collisional activation, several characteristic fragment ions are produced and their fragmentation mechanisms are rationalized by electrophilic aromatic substitution accompanied by benzyl cation transfer. (1) For N-(p-methoxybenzylidene)-1-phenylmethanimine, concomitant with a loss of HCN, a product ion at m/z 121 was observed. It is proposed to be generated from electrophilic substitution at the ipso-position by transferring benzyl cation rather than cleavage of the C-N double bond. (2) For N-(m-methoxybenzylidene)-1-phenylmethanimine, a product ion at m/z 209 was obtained, corresponding to the elimination of NH(3) carrying two hydrogens from the two aromatic rings respectively. This process can be rationalized by two sequential electrophilic substitutions and cyclodeamination reaction based on the benzyl cation transfer. Deuterium-labeled experiments, density functional theory (DFT) calculation and substituent effect results also corroborate the proposed mechanism.

Characterization of multiple fragmentation pathways initiated by collision‐induced dissociation of multifunctional anions formed by deprotonation of 2‐nitrobenzenesulfonylglycine

The correlation of anion structure with the fragmentation behavior of deprotonated nitrobenzenesulfonylamino acids was investigated using tandem mass spectrometry, isotopic labeling and computational methods. Four distinct fragmentation pathways resulting from the collision-induced dissociation (CID) of deprotonated 2-nitrobenzenesulfonylglycine (NsGly) were characterized. The unusual loss of the aryl nitro substituent as HONO was the lowest energy process. Subsequent successive losses of CO, HCN and SO2 indicated that an ortho cyclization reaction had accompanied loss of HONO. Other pathways involving rearrangement of the ionized sulfonamide group, dual bond cleavage and intramolecular nucleophilic displacement were proposed to account for the formation of phenoxide, arylsulfinate and arylsulfonamide product ions at higher collision energies. The four distinct fragmentation pathways were consistent with precursor-product relationships established by CID experiments, isotopic labeling results and the formation of analogous product ions from 2,4-dinitrobenzenesulfonylglycine and the Ns derivatives of alanine and 2-aminoisobutyric acid. The computations confirmed a low barrier for ortho cyclization with loss of HONO and feasible energetics for each reaction step in the four pathways. Computations also indicated that three of the fragmentation pathways started from NsGly ionized at the carboxyl group. Overall, the pathways identified for the fragmentation of the NsGly anion differed from processes reported for anions containing a single functional group, demonstrating the importance of functional group interactions in the fragmentation pathways of multifunctional anions.

Regioselectivity of the intramolecular nucleophilic attack in [R[sbnd]CH−[sbnd]N[dbnd]CH[sbnd]C6H4[sbnd]Y]: A mass spectrometric and computational study

The investigation into the intramolecular nucleophilic attack in carbanion [RCH −NCHC6H4Y] in the gas phase has been carried out by mass spectrometry and density functional theory (DFT). The main results of the present work are as follows: the regioselectivity of the intramolecular attack depends on the substituent on the para-position of the benzene ring. NO2 favors C3-attack to form spiro-σ-adduct and it also contributes to the loss of HCN, while other substituents (H, OMe, NMe2 and Cl) favor C4-attack to yield bicyclo-σ-adduct and in this condition, HCN cannot be lost. In the meantime, DFT calculations also demonstrate that the loss of HCN from the spiro-σ-adduct is both thermodynamically and kinetically beneficial, while that from the bicyclo-σ-adduct is disadvantageous either in kinetics or thermodynamics.

Gas-phase cleavage of the novel iminium ions [R1[sbnd]CH+[sbnd]N[dbnd]CH[sbnd]R2 ↔ R1[sbnd]CH[dbnd]N+[dbnd]CH[sbnd]R2]: An experimental and computational study

The preparation of the novel iminium ions [R1CH+NCHR2↔R1CHN+CHR2] and mechanistic study of their gas-phase reactions have been carried out by mass spectrometry and density functional theory. DFT calculations show that this kind of iminium ion is similar to the allene in structure. Two main reaction pathways have been assumed: one is the simple cleavage, including homolytic and heterolytic cleavages of the CC bond; the other might be the intramolecular cyclization, which is supported by the loss of HCN.

Gas-phase spectroscopy of protonated adenine, adenosine 5′-monophosphate and monohydrated ions

Microsolvation of chromophore ions commonly has large effects on their electronic structure and as a result on their optical absorption spectra. Here spectroscopy of protonated adenine (AdeH(+)) and its complex with one water molecule isolated in vacuo was done using a home-built mass spectrometer in combination with a tuneable pulsed laser system. Experiments also included the protonated adenosine 5'-monophosphate nucleotide (AMPH(+)). In the case of bare AdeH(+) ions, one-photon absorption leads to four dominant fragment ions corresponding to ammonium and ions formed after loss of either NH3, HCN, or NH2CN. The yields of these were measured as a function of the wavelength of the light from 210 nm to 300 nm, and they were combined to obtain the total photoinduced dissociation at each wavelength (i.e., action spectrum). A broad band between 230 nm and 290 nm and the tail of a band with maximum below 210 nm (high-energy band) are seen. In the case of AdeH(+)(H2O), the dominant dissociation channel after photoexcitation in the low-energy band was simply loss of H2O while photodissociation of protonated AMP revealed two dominant dissociation channels associated with the formation of either AdeH(+) or loss of H3PO4. The action spectra of AdeH(+), AdeH(+)(H2O), and AMPH(+) are almost identical in the 230-290 nm region, and they resemble the absorption spectrum of protonated adenine in aqueous solution recorded at low pH. Hence from our work it is firmly established that the lowest-energy transitions are independent of the surroundings.

Loss of HCN from the Pyrimidine Molecular Ion: A Computational Study

Department of Chemistry, Seoul National University, Seoul 151-742, KoreaReceived August 31, 2012, Accepted September 25, 2012The potential energy surface (PES) for the loss of HCN from the pyrimidine molecular ion has been exploredusing quantum chemical calculations. Possible reaction pathways to form five C

Anion chemistry on Titan: A possible route to large N-bearing hydrocarbons

The reaction of CN− with cyanoacetylene (HC3N), has been studied as a function of the HC3N pressure in a quadrupole tandem mass spectrometer. The mass spectra revealed the fast depletion of the CN− parent ion and formation of larger anions of rapidly growing size. Most of the ions observed were found to belong to two series of products: (HC3N)x·C2p+1N− and (HC3N)x·C2pN− resulting from the sequential additions of HC3N molecules and loss of HCN or HCCN molecules. The mechanism and energetics of the first two reaction steps are briefly discussed. The laboratory data are compared with those from the Cassini CAPS-ELS spectrometer. It is believed that the reactions observed could account for the growth of anions in Titan’s ionosphere.

Modelling peptide–metal dication interactions: formamide–Ca2+ reactions in the gas phase

The collision induced dissociation of formamide-Ca(2+) complexes produced in the gas phase through nanoelectrospray ionization yields as main products ions [CaOH](+), [HCNH](+), [Ca(NH(2))](+), HCO(+) and [Ca(NH(3))](2+) and possibly [Ca(H(2)O)](2+) and [C,O,Ca](2+), the latter being rather minor. The mechanisms behind these fragmentation processes have been established by analyzing the topology of the potential energy surface by means of B3LYP calculations carried out with a core-correlated cc-pWCVTZ basis set. The Ca(2+) complexes formed by formamide itself and formimidic acid play a fundamental role. The former undergoes a charge separation reaction yielding [Ca(NH(2))](+) + HCO(+), and the latter undergoes the most favorable Coulomb explosion yielding [Ca-OH](+) + [HCNH](+) and is the origin of a multistep mechanism which accounts for the observed loss of water and HCN. Conversely, the other isomer of formamide, amino(hydroxyl)carbene, does not play any significant role in the unimolecular reactivity of the doubly charged molecular cation.

Unimolecular dissociation of anthracene and acridine cations: The importance of isomerization barriers for the C2H2 loss and HCN loss channels

The loss of C(2)H(2) is a low activation energy dissociation channel for anthracene (C(14)H(10)) and acridine (C(13)H(9)N) cations. For the latter ion another prominent fragmentation pathway is the loss of HCN. We have studied these two dissociation channels by collision induced dissociation experiments of 50 keV anthracene cations and protonated acridine, both produced by electrospray ionization, in collisions with a neutral xenon target. In addition, we have carried out density functional theory calculations on possible reaction pathways for the loss of C(2)H(2) and HCN. The mass spectra display features of multi-step processes, and for protonated acridine the dominant first step process is the loss of a hydrogen from the N site, which then leads to C(2)H(2)/HCN loss from the acridine cation. With our calculations we have identified three pathways for the loss of C(2)H(2) from the anthracene cation, with three different cationic products: 2-ethynylnaphthalene, biphenylene, and acenaphthylene. The third product is the one with the overall lowest dissociation energy barrier. For the acridine cation our calculated pathway for the loss of C(2)H(2) leads to the 3-ethynylquinoline cation, and the loss of HCN leads to the biphenylene cation. Isomerization plays an important role in the formation of the non-ethynyl containing products. All calculated fragmentation pathways should be accessible in the present experiment due to substantial energy deposition in the collisions.

Loss of HCN from the Pyrazine Molecular Ion: A Theoretical Study

The potential energy surface (PES) for the loss of HCN or HNC from the pyrazine molecular ion was determined based on quantum chemical calculations using the G3//B3LYP method. Four possible dissociation pathways to form four isomers were examined. A Rice-Ramsperger-Kassel-Marcus quasi-equilibrium theory model calculation was performed to predict the dissociation rate constant and the product branching ratio on the basis of the obtained PES. The resultant rate constant for the HCN loss agreed with the previous experimental result. The kinetic analysis predicted that the formation of was predominant, which occurred by three consecutive steps, a C-C bond cleavage to form a linear intermediate, a rearrangement to form an H-bridged intermediate, and elimination of HCN.

Formation of C4H4•+ from the Pyridine Radical Cation: A Theoretical Mechanistic and Kinetic Study

The potential energy surface (PES) for the formation of C(4)H(4)(•+) from the pyridine radical cation by loss of HCN was determined from quantum chemical calculations using the G3//B3LYP method. The complete reaction pathways for the formation of the low-energy C(4)H(4)(•+) isomers, radical cations of methylenecyclopropene (MCP(•+)), vinylacteylene (VA(•+)), cyclobutadiene, and butatriene were obtained. Based on the PESs, a Rice-Ramsperger-Kassel-Marcus model calculation was performed to investigate the dissociation kinetics. The calculated dissociation rate constants agreed with the previous experimental data. It was predicted that a mixture of MCP(•+) and VA(•+) was formed by loss of HCN. The formation of MCP(•+) was more favored near the dissociation threshold and at high energies, whereas the formation of VA(•+) was more favored at the low energies corresponding to the ion lifetime of microseconds.

The covalently bound dimer ion HC[dbnd]N[sbnd]C[dbnd]NH[rad]+ and its neutral counterpart

Model chemistry calculations (CBS-QB3 and CBS-APNO methods) and tandem mass spectrometry based experiments indicate that dissociative ionization of 2-methoxy-s-triazine (consecutive losses of CH2O and HCN) yields the elusive covalently bound [H,C,N] dimer ion HCNCNH+, a species of interest in astrochemistry. Neutralization–Reionization Mass Spectrometry (NRMS) experiments indicate that its neutral counterpart, HCNCNH, is a kinetically stable molecule in the rarefied gas-phase.

Fire effluent component yields from room‐scale fire tests

AbstractEstimation of the time available for escape (ASET) in the event of a fire is a principal component in fire hazard or risk assessment. Valid data on the yields of toxic smoke components from bench‐scale apparatus is essential to accurate ASET calculations. This paper presents a methodology for obtaining pre‐flashover and post‐flashover toxicant yields from room‐scale fire tests. The data are to be used for comparison with bench‐scale data for the same combustibles: a sofa, bookcases, and electric power cable. Each was burned in a room with a long adjacent corridor. The yields of CO2, CO, HCl, HCN, and soot were determined. Other toxicants (NO2, formaldehyde, and acrolein), whose concentrations were below the detection limits, were of limited importance relative to the detected toxicants. The uncertainty values were comparable to those estimated for calculations used to determine ASET and were sufficiently small to determine whether a bench‐scale apparatus is producing results that are similar to the real‐scale results here. The use of Fourier transform infrared spectroscopy was useful for obtaining toxicant concentration data; however, its operation and interpretation are not routine. The losses of CO, HCN, and HCl along the corridor were dependent on the combustible. Copyright © 2009 John Wiley & Sons, Ltd.

The covalently bound HC [tbnd]N dimer ions HC [dbnd]N−N [dbnd]CH [rad]+ and HC [dbnd]N−C( [dbnd]N)H [rad]+ are stable species in the gas-phase, but the neutral counterparts are not

Tandem mass spectrometry based experiments and computational chemistry (CBS-QB3/APNO methods) indicate that ionized s-tetrazine eliminates N 2 to yield the elusive linear HC N dimer ion HC N–N CH + ( 1). The ion is stable in the rarefied gas-phase but, as it is generated with considerable internal energy, it readily interconverts with HC N–C( N)H + ( 2), via a 1,2-HCN shift. This more stable HCN dimer ion was generated independently by loss of HCN from ionized s-triazine. Whereas the HN C dimer ion HN C C NH + has a (kinetically) stable neutral counterpart, theory and experiment (neutralization–reionization mass spectrometry) agree that the HC N dimer ions 1 and 2 do not.

ESI-MS spectra of 3-cyano-4-(substituted phenyl)-6-phenyl-2(1H)-pyridinones

Twelve 3-cyano-4-(substituted phenyl)-6-phenyl-2(1H)-pyridinones were investigated by tandem mass spectrometry using positive as well as negative electrospray ionization. The influence of the electron affinity of the substituent and the steric effect on the fragmentation is discussed. Pyridinones with a substituent of low proton affinity show loss of water, HCN or benzene from the pyridinone ring in the first step of MS2 fragmentations. Oppositely, if a substituent with high proton affinity is present on the phenyl ring in the 4-position of pyridinone, the fragmentation paths are complex, depending mainly on the substituent proton acceptor ability. Elimination of neutral molecules CO, HCN, H2O, PhH (benzene) or Ph and CN radicals are fragmentation processes common for all compounds in the subsequent steps of the fragmentations.

Ni+Reactions with Aminoacrylonitrile, A Species of Potential Astrochemical Relevance

The reaction of aminoacrylonitrile, a species of astrochemical interest, with Ni(+)((2)D(5/2)) was investigated by means of mass spectrometry techniques and density functional theory calculations. The dominant fragmentations in the MIKE spectrum correspond to the loss of [C2,N,H3], HCN, and NH3, the loss of H2 being very minor. The structure and bonding of the different aminoacrylonitrile-Ni(+) complexes were investigated at the B3LYP/6-311G(d,p) level of theory. The same approach was employed in our survey of the corresponding potential energy surface. This survey indicates that the [C2,N,H3] neutral product can be formed either as ketenimine (CH2CNH) or acetonitrile. The formation of the latter is significantly more exothermic but involves slightly higher activation barriers; so very likely, both isomers are produced along the reaction process. The lost of HNC is not competitive with the loss of HCN, because when the former is formed the products lie higher in energy and the corresponding mechanisms involve energy barriers above the entrance channel. The loss of NH3 is associated with the formation of a complex between cyanoacetylene, HCCCN, which is very abundant in the interstellar media, and Ni(+).

The Role of Long-Range Forces in the Determination of Translational Kinetic Energy Release. Loss of C4H4+ from the Benzene and Pyridine Cations

Kinetic energy release distributions (KERDs) for the benzene ion fragmenting into C 4H 4 (+) and C 2H 2 have been recorded by double-focusing mass spectrometry in the metastable energy window and by a retarding field experiment up to an energy of 5 eV above the fragmentation threshold. They are compared with those resulting from the HCN loss reaction from the pyridine ion. Both reactions display a similar variation of the kinetic energy release as a function of the internal energy: the average release is smaller than statistically expected, with a further restriction of the phase-space sampling for the C 5H 5N (+) dissociation. Ab initio calculations of the potential-energy profile have been carried out. They reveal a complicated reaction mechanism, the last step of which consists in the dissociation of a weakly bound ion-quadrupole or ion-dipole complex. The KERDs have been analyzed by the maximum entropy method. The fraction of phase space effectively sampled by the pair of fragments has been determined and is similar for both dissociations. Both reactions are constrained by the square root of the released translational energy, epsilon (1/2). This indicates that in the latter stage of the dissociation process, the reaction coordinate is adiabatically decoupled from the bath of the bound degrees of freedom. For the C 6H 6 (+) fragmentation, the analysis of the experimental results strongly suggests that, just as for a spherically symmetric interaction potential, the translational motion is confined to a plane. For the dissociation of the pyridine ion, the main dynamical constraint is also a restriction to a two-dimensional subspace. This dimensionality reduction of the translational phase space is due to the fact that the Hamiltonian of both weakly bound complexes contains a cyclic coordinate.

Ni+reactions with aminoacetonitrile, a potential prebiological precursor of glycine

The gas-phase reactions between Ni(+) ((2)D(5/2)) and aminoacetonitrile, a molecule of prebiological interest as possible precursor of glycine, have been investigated by means of mass spectrometry techniques. The mass-analyzed ion kinetic energy (MIKE) spectrum reveals that the adduct ions [NC--CH(2)--NH(2), Ni(+)] spontaneously decompose by loosing HCN, H(2), and H(2)CNH, the loss of hydrogen cyanide being clearly dominant. The structures and bonding characteristics of the aminoacetonitrile-Ni(+) complexes as well as the different stationary points of the corresponding potential energy surface (PES) have been theoretically studied by density functional theory (DFT) calculations carried out at B3LYP/6-311G(d,p) level. A cyclic intermediate, in which Ni(+) is bisligated to the cyano and the amino group, plays an important role in the unimolecular reactivity of these ions, because it is the precursor for the observed losses of HCN and H(2)CNH. In all mechanisms associated with the loss of H(2), the metal acts as hydrogen carrier favoring the formation of the H(2) molecule. The estimated bond dissociation energy of aminoacetonitrile-Ni(+) complexes (291 kJ mol(-1)) is larger than those measured for other nitrogen bases such as pyridine or pyrimidine and only slightly smaller than that of adenine.

Gas Phase Reaction of Substituted Isoquinolines to Carboxylic Acids in Ion Trap and Triple Quadrupole Mass Spectrometers after Electrospray Ionization and Collision-Induced Dissociation

Within the mass spectrometric study of bisubstituted isoquinolines that possess great potential as prolylhydroxylase inhibitor drug candidates (e.g., FG-2216), unusually favored gas-phase formations of carboxylic acids after collisional activation were observed. The protonated molecule of [(1-chloro-4-hydroxy-isoquinoline-3-carbonyl)-amino]-acetic acid was dissociated, yielding the 1-chloro-4-hydroxy-isoquinoline-3-carboxylic acid methyleneamide cation. Subsequent dissociation caused the nominal elimination of 11 u that resulted from the loss of HCN and concomitant addition of oxygen to the product ion, which formed the protonated 1-chloro-4-hydroxy-isoquinoline-3-carboxylic acid. The preference of this structure under mass spectrometric conditions was substantiated by tandem mass spectrometry analyses using the corresponding methyl ester (1-chloro-4-hydroxy-isoquinoline-3-carboxylic acid methyl ester) that eliminated methylene (-14 u) upon collisional activation. Moreover, the major product ion of 1-chloro-4-hydroxy-isoquinoline-3-carboxylic acid, which resulted from the loss of water in MS3 experiments, restored the precursor ion structure by re-addition of H2O. Evidences for these phenomena were obtained by chemical synthesis of proposed gas-phase intermediates, H/D exchange experiments, high-resolution/high accuracy mass spectrometry at MSn level, and "ping-pong" analyses (MS7, in which the precursor ion was dissociated and the respective product ion isolated to regenerate the precursor ion for repeated dissociation. Based on these results, dissociation pathways for [(1-chloro-4-hydroxy-isoquinoline-3-carbonyl)-amino]-acetic acid were suggested that can be further utilized for the characterization of structurally related compounds or metabolic products in clinical, forensic, or doping control analysis.

Die Tetracyanoborsäuren H[B(CN)4]·n H2O, n = 0, 1, 2

AbstractThe Tetracyanoboronic Acids H[B(CN)4]·n H2O, n = 0, 1, 2Treatment of an aqueous solution of Na[B(CN)4] with an acidic cation exchange resin leads to a solution of the strong tetracyanoboronic acid. Evaporation of the solution at room temperature yields colourless single crystals of [H5O2][B(CN)4] ($P{\bar 4}n {\rm 2}$, a = 9.5830(2) Å, c = 14.25440(3) Å, Z = 1). Further drying of [H5O2][B(CN)4] (mp. 115 °C) in vacuum at 50 °C gives polycrystalline [H3O][B(CN)4] (P63mc, a = 8.704(1) Å, c = 6.152(1) Å, Z = 2), which is thermally stable up to 145 °C. The anhydrous polycrystalline acid H[B(CN)4] is formed quantitatively by reacting Me3SiNCB(CN)3 with gaseous HCl. This acid starts to decompose at 190 °C with loss of HCN. All three acids were further characterized by vibrational spectroscopy, and elemental analysis.