Five vs. six membered-ring PAH products from reaction of o-methylphenyl radical and two C3H4 isomers.

Gas-phase reactions of the o-methylphenyl (o-CH3C6H4) radical with the C3H4 isomers allene (H2C[double bond, length as m-dash]C[double bond, length as m-dash]CH2) and propyne (HC[triple bond, length as m-dash]C-CH3) are studied at 600 K and 4 Torr (533 Pa) using VUV synchrotron photoionisation mass spectrometry, quantum chemical calculations and RRKM modelling. Two major dissociation product ions arise following C3H4 addition: m/z 116 (CH3 loss) and 130 (H loss). These products correspond to small polycyclic aromatic hydrocarbons (PAHs). The m/z 116 signal for both reactions is conclusively assigned to indene (C9H8) and is the dominant product for the propyne reaction. Signal at m/z 130 for the propyne case is attributed to isomers of bicyclic methylindene (C10H10) + H, which contains a newly-formed methylated five-membered ring. The m/z 130 signal for allene, however, is dominated by the 1,2-dihydronaphthalene isomer arising from a newly created six-membered ring. Our results show that new ring formation from C3H4 addition to the methylphenyl radical requires an ortho-CH3 group - similar to o-methylphenyl radical oxidation. These reactions characteristically lead to bicyclic aromatic products, but the structure of the C3H4 co-reactant dictates the structure of the PAH product, with allene preferentially leading to the formation of two six-membered ring bicyclics and propyne resulting in the formation of six and five-membered bicyclic structures.

C14H10 polycyclic aromatic hydrocarbon formation by acetylene addition to naphthalenyl radicals observed.

The formation of polycyclic aromatic hydrocarbons (PAHs) during combustion has a substantial impact on environmental pollution and public health. The hydrogen-abstraction-acetylene-addition (HACA) mechanism is expected to be a significant source of larger PAHs containing more than two rings. In this study, the reactions of 1-naphthalenyl and 2-naphthalenyl radicals with acetylene (C2H2) are investigated using VUV photoionization time-of-flight mass spectrometry at 500 to 800 K, 15 to 50 torr, and reaction times up to 10 ms. Our experimental conditions allow us to probe the Bittner-Howard and modified Frenklach HACA routes, but not routes that require multiple radicals to drive the chemistry. The kinetic measurements are compared to a temperature-dependent kinetic model constructed using quantum chemistry calculations and accounting for chemical-activation and fall-off effects. We measure significant quantities of C14H10 (likely phenanthrene and anthracene), as well as 2-ethynylnaphthalene (C12H8), from the reaction of the 2-naphthalenyl radical with C2H2; these results are consistent with the predictions of the kinetic model and the HACA mechanism, but contradict a previous experimental study that indicated no C14H10 formation in the 2-naphthalenyl + C2H2 reaction. In the 1-naphthalenyl radical + C2H2 reaction system, the primary product measured is C12H8, consistent with the predicted formation of acenaphthylene via HACA. The present work provides direct experimental evidence that single-radical HACA can be an important mechanism for the formation of PAHs larger than naphthalene, validating a common assumption in combustion models.

Synthesis of Polycyclic Aromatic Hydrocarbons by Phenyl Addition-Dehydrocyclization: The Third Way.

Polycyclic aromatic hydrocarbons (PAHs) represent the link between resonance-stabilized free radicals and carbonaceous nanoparticles generated in incomplete combustion processes and in circumstellar envelopes of carbon rich asymptotic giant branch (AGB) stars. Although these PAHs resemble building blocks of complex carbonaceous nanostructures, their fundamental formation mechanisms have remained elusive. By exploring these reaction mechanisms of the phenyl radical with biphenyl/naphthalene theoretically and experimentally, we provide compelling evidence on a novel phenyl-addition/dehydrocyclization (PAC) pathway leading to prototype PAHs: triphenylene and fluoranthene. PAC operates efficiently at high temperatures leading through rapid molecular mass growth processes to complex aromatic structures, which are difficult to synthesize by traditional pathways such as hydrogen-abstraction/acetylene-addition. The elucidation of the fundamental reactions leading to PAHs is necessary to facilitate an understanding of the origin and evolution of the molecular universe and of carbon in our galaxy.

Product detection study of the gas-phase oxidation of methylphenyl radicals using synchrotron photoionisation mass spectrometry.

Product detection studies of the gas-phase oxidation of o-methylphenyl radicals and m-methylphenyl radicals are reported at ambient temperature (ca. 298 K) and 4 Torr (533.3 Pa) using VUV synchrotron photoionisation mass spectrometry. It is shown that cyclopentadienone (c-C5H4[double bond, length as m-dash]O) + CH3CO and o-quinone methide (o-CH2[double bond, length as m-dash]C6H4[double bond, length as m-dash]O) + OH are unique product pathways to the o-methylphenyl + O2 reaction due to mechanisms requiring the CH3 group to be adjacent to the phenyl radical site. Common product pathways include methylphenoxy radical + O(3P) and isomers of methylcyclopentadienone (CH3C5H4[double bond, length as m-dash]O) + HCO. G3X-K quantum chemical calculations are deployed to rationalise experimental results for o-methylphenyl and m-methylphenyl radical oxidation. The o-quinone methide formation mechanism from o-methylphenyl + O2 is analogous to the formation of o-benzoquinone from o-hydroxyphenyl + O2 where, after O2 addition, the ortho-substituent in the phenylperoxyl intermediate undergoes a 1,5-H shift and eliminates OH. Other reaction products, including methylcyclopentadienone species and methylphenyoxy radicals, are rationalised by applying known phenyl oxidation mechanisms. Transition state bifurcations are present in both radical systems and have exclusive end products (with different molecular mass). Compared to previous o-hydroxyphenyl and charged-tagged methylphenyl radical oxidation studies, there are significantly more products owing to the activation in this radical system and the competitiveness of rate limiting pathways.

Reactivity of the Indenyl Radical (C9 H7 ) with Acetylene (C2 H2 ) and Vinylacetylene (C4 H4 ).

The reactions of the indenyl radicals with acetylene (C2 H2 ) and vinylacetylene (C4 H4 ) is studied in a hot chemical reactor coupled to synchrotron based vacuum ultraviolet ionization mass spectrometry. These experimental results are combined with theory to reveal that the resonantly stabilized and thermodynamically most stable 1-indenyl radical (C9 H7. ) is always formed in the pyrolysis of 1-, 2-, 6-, and 7-bromoindenes at 1500 K. The 1-indenyl radical reacts with acetylene yielding 1-ethynylindene plus atomic hydrogen, rather than adding a second acetylene molecule and leading to ring closure and formation of fluorene as observed in other reaction mechanisms such as the hydrogen abstraction acetylene addition or hydrogen abstraction vinylacetylene addition pathways. While this reaction mechanism is analogous to the bimolecular reaction between the phenyl radical (C6 H5. ) and acetylene forming phenylacetylene (C6 H5 CCH), the 1-indenyl+acetylene→1-ethynylindene+hydrogen reaction is highly endoergic (114 kJ mol-1 ) and slow, contrary to the exoergic (-38 kJ mol-1 ) and faster phenyl+acetylene→phenylacetylene+hydrogen reaction. In a similar manner, no ring closure leading to fluorene formation was observed in the reaction of 1-indenyl radical with vinylacetylene. These experimental results are explained through rate constant calculations based on theoretically derived potential energy surfaces.

Gas-Phase Oxidation of the Protonated Uracil-5-yl Radical Cation.

This study targets the kinetics and product detection of the gas-phase oxidation reaction of the protonated 5-dehydrouracil (uracil-5-yl) distonic radical cation using ion-trap mass spectrometry. Protonated 5-dehydrouracil radical ions (5-dehydrouracilH+ radical ion, m/z 112) are produced within an ion trap by laser photolysis of protonated 5-iodouracil. Storage of the 5-dehydrouracilH+ radical ion in the presence of controlled concentration of O2 reveals two main products. The major reaction product pathway is assigned as the formation of protonated 2-hydroxypyrimidine-4,5-dione (m/z 127) + •OH. A second product ion (m/z 99), putatively assigned as a five-member-ring ketone structure, is tentatively explained as arising from the decarbonylation (-CO) of protonated 2-hydroxypyrimidine-4,5-dione. Because protonation of the 5-dehydrouracil radical likely forms a dienol structure, the O2 reaction at the 5 position is ortho to an -OH group. Following this addition of O2, the peroxyl-radical intermediate isomerizes by H atom transfer from the -OH group. The ensuing hydroperoxide then decomposes to eliminate •OH radical. It is shown that this elimination of •OH radical (-17 Da) is evidence for the presence of an -OH group ortho to the initial phenyl radical site, in good accord with calculations. The subsequent CO loss mechanism, to form the aforementioned five-member-ring structure, is unclear, but some pathways are discussed. By following the kinetics of the reaction, the room temperature second-order rate coefficient of the 5-dehydrouracilH+ distonic radical cation with molecular oxygen is measured at 7.2 × 10-11 cm3 molecule-1 s-1, Φ = 12% (with ±50% total accuracy). For aryl radical reactions with O2, the presence of the •OH elimination product pathway, following the peroxyl-radical formation, is an indicator of an -OH group ortho to the radical site.

Highly efficient gas-phase reactivity of protonated pyridine radicals with propene.

Small nitrogen containing heteroaromatics are fundamental building blocks for many biological molecules, including the DNA nucleotides. Pyridine, as a prototypical N-heteroaromatic, has been implicated in the chemical evolution of many extraterrestrial environments, including the atmosphere of Titan. This paper reports on the gas-phase ion-molecule reactions of the three dehydro-N-pyridinium radical cation isomers with propene. Photodissociation ion-trap mass spectrometry experiments are used to measure product branching ratios and reaction kinetics. Reaction efficiencies for 2-dehydro-N-pyridinium, 3-dehydro-N-pyridinium and 4-dehydro-N-pyridinium with propene are 70%, 47% and 41%, respectively. The m/z 106 channel is the major product channel across all cases and assigned 2-, 3-, and 4-vinylpyridinium for each reaction. The m/z 93 channel is also significant and assigned the 2-, 3-, and 4-N-protonated-picolyl radical cation for each case. H-Abstraction from propene is not competitive under experimental conditions. Potential energy schemes, at the M06-2X/6-31(2df,p) level of theory and basis set, are described to assist in rationalising observed product branching ratios and elucidating possible reaction mechanisms. Reaction barriers to the production of vinylpyridinium (m/z 106) + CH3 are the lowest identified for the 3- and 4-dehydro-N-pyridinium reactions, in support of the observed dominance of the m/z 106 ion signal. Ethylene loss via ring-mediated H-transfer along the propyl group is found to be the lowest energy pathway for the 2-dehydro-N-pyridinium reaction, suggesting a preference toward m/z 93 (N-protonated-picolyl radical cation) over the experimentally observed products. Entropic bottle-necks along the m/z 93 pathway however, associated with ring-mediated H-atom transfer, are responsible for the dominance of m/z 106 in the 2-dehydro-N-pyridinium + propene reaction. For all three isomers, computed barriers for all observed reaction channels were below the entrance channel, suggesting these reactions can contribute to molecular weight growth in extraterrestrial environments with accelerated reaction rates in low temperature regions of space.

Formation and stability of gas-phase o-benzoquinone from oxidation of ortho-hydroxyphenyl: a combined neutral and distonic radical study.

Gas-phase product detection studies of o-hydroxyphenyl radical and O2 are reported at 373, 500, and 600 K, at 4 Torr (533.3 Pa), using VUV time-resolved synchrotron photoionisation mass spectrometry. The dominant products are assigned as o-benzoquinone (C6H4O2, m/z 108) and cyclopentadienone (C5H4O, m/z 80). It is concluded that cyclopentadienone forms as a secondary product from prompt decomposition of o-benzoquinone (and dissociative ionization of o-benzoquinone may contribute to the m/z 80 signal at photon energies ≳9.8 eV). Ion-trap reactions of the distonic o-hydroxyphenyl analogue, the 5-ammonium-2-hydroxyphenyl radical cation, with O2 are also reported and concur with the assignment of o-benzoquinone as the dominant product. The ion-trap study also provides support for a mechanism where cyclopentadienone is produced by decarbonylation of o-benzoquinone. Kinetic studies compare oxidation of the ammonium-tagged o-hydroxyphenyl and o-methylphenyl radical cations along with trimethylammonium-tagged analogues. Reaction efficiencies are found to be ca. 5% for both charge-tagged o-hydroxyphenyl and o-methylphenyl radicals irrespective of the charged substituent. G3X-K quantum chemical calculations are deployed to rationalise experimental results for o-hydroxyphenyl + O2 and its charge-tagged counterpart. The prevailing reaction mechanism, after O2 addition, involves a facile 1,5-H shift in the peroxyl radical and subsequent elimination of OH to yield o-benzoquinone that is reminiscent of the Waddington mechanism for ß-hydroxyperoxyl radicals. These results suggest o-hydroxyphenyl + O2 and decarbonylation of o-benzoquinone serve as plausible OH and CO sources in combustion.

Hydroxyl radical formation in the gas phase oxidation of distonic 2-methylphenyl radical cations.

The reactions of distonic 4-(N,N,N-trimethylammonium)-2-methylphenyl and 5-(N,N,N-trimethylammonium)-2-methylphenyl radical cations (m/z 149) with O2 are studied in the gas phase using ion-trap mass spectrometry. Photodissociation (PD) of halogenated precursors gives rise to the target distonic charge-tagged methylphenyl radical whereas collision-induced dissociation (CID) is found to produce unreactive radical ions. The PD generated distonic radicals, however, react rapidly with O2 to form [M + O2]˙(+) and [M + O2- OH]˙(+) ions, detected at m/z 181 and m/z 164, respectively. Quantum chemical calculations using G3SX(MP3) and M06-2X theories are deployed to examine key decomposition pathways of the 5-(N,N,N-trimethylammonium)-2-methylphenylperoxyl radical and rationalise the observed product ions. The prevailing product mechanism involves a 1,5-H shift in the peroxyl radical forming a QOOH-type intermediate that subsequently eliminates ˙OH to yield charge-tagged 2-quinone methide. Our study suggests that the analogous process should occur for the neutral methylphenyl + O2 reaction, thus serving as a plausible source of ˙OH radicals in combustion environments.

Product branching fractions of the CH + propene reaction from synchrotron photoionization mass spectrometry.

The CH(X(2)Π) + propene reaction is studied in the gas phase at 298 K and 4 Torr (533.3 Pa) using VUV synchrotron photoionization mass spectrometry. The dominant product channel is the formation of C4H6 (m/z 54) + H. By fitting experimental photoionization spectra to measured spectra of known C4H6 isomers, the following relative branching fractions are obtained: 1,3-butadiene (0.63 ± 0.13), 1,2-butadiene (0.25 ± 0.05), and 1-butyne (0.12 ± 0.03) with no detectable contribution from 2-butyne. The CD + propene reaction is also studied and two product channels are observed that correspond to C4H6 (m/z 54) + D and C4H5D (m/z 55) + H, formed at a ratio of 0.4 (m/z 54) to 1.0 (m/z 55). The D elimination channel forms almost exclusively 1,2-butadiene (0.97 ± 0.20) whereas the H elimination channel leads to the formation of deuterated 1,3-butadiene (0.89 ± 0.18) and 1-butyne (0.11 ± 0.02); photoionization spectra of undeuterated species are used in the fitting of the measured m/z 55 (C4H5D) spectrum. The results are generally consistent with a CH cycloaddition mechanism to the C═C bond of propene, forming 1-methylallyl followed by elimination of a H atom via several competing processes. The direct detection of 1,3-butadiene as a reaction product is an important validation of molecular weight growth schemes implicating the CH + propene reaction, for example, those reported recently for the formation of benzene in the interstellar medium (Jones , B. M. Proc. Natl. Acad. Sci. U.S.A. 2011 , 108 , 452 - 457).