Fulvenallenyl Radical (C7H5·)-Mediated Gas-Phase Synthesis of Bicyclic Aromatic C10H8 Isomers: Can Fulvenallenyl Efficiently React with Closed-Shell Hydrocarbons?

To understand the reactivity of resonantly stabilized radicals, often found in relevant concentrations in gaseous environments, it is important to determine their main reaction pathways. Here, it is investigated whether the fulvenallenyl radical (C7H5·) reacts preferentially with closed-shell molecules or radicals. Electronic structure calculations on the C10H9 potential energy surface accessed by the reactions of C7H5· with methylacetylene (CH3CCH) and allene (H2CCCH2) were combined with RRKM-ME calculations of temperature- and pressure-dependent rate constants using the automated EStokTP software suite and kinetic modeling to assess the reactivity of C7H5· with closed-shell unsaturated hydrocarbons. Experimentally, the reactions were attempted in a chemical microreactor heated to 998 ± 10 K by preparing fulvenallenyl radicals via pyrolysis of trichloromethylbenzene (C7H5Cl3) and seeding the radicals in methylacetylene or allene carrier gas, with product identification by means of photoionization mass spectrometry. The measured photoionization efficiency curve of m/z = 128 was assigned to a linear combination of the reference curves of two C10H8 isomers, azulene (minor) and naphthalene (major), presumably resulting from the C7H5· plus C3H4 reactions. However, the calculations demonstrated that these reactions are too slow, and kinetic modeling of processes in the reactor allowed us to conclude that the observation of naphthalene and azulene is due to the C7H5· plus C3H3· reaction, where propargyl is produced by direct hydrogen atom abstraction by chlorine (Cl) atoms from allene or methylacetylene and Cl stem from the pyrolysis of C7H5Cl3. Modeling results under the copyrolysis conditions of toluene and methylacetylene in high-temperature shock tube experiments confirmed the prevalence of the fulvenallenyl reaction with propargyl over its reactions with C3H4 even when the concentrations of allene and methylacetylene largely exceed that of propargyl. Overall, the reactions of fulvenallenyl with both allene and methylacetylene were found to be noncompetitive in the formation of naphthalene and azulene thus attesting the inefficiency of the fulvenallenyl radical reactions with the prototype closed-shell hydrocarbon species. In the meantime, the new reaction pathways revealed, including H-assisted isomerizations between C10H8 isomers and decomposition reactions of various C10H9 isomers, emerge as relevant and are recommended for inclusion in combustion kinetic models for naphthalene formation.

Exploring the chemical dynamics of phenanthrene (C14H10) formation via the bimolecular gas-phase reaction of the phenylethynyl radical (C6H5CC) with benzene (C6H6).

The exploration of the fundamental formation mechanisms of polycyclic aromatic hydrocarbons (PAHs) is crucial for the understanding of molecular mass growth processes leading to two- and three-dimensional carbonaceous nanostructures (nanosheets, graphenes, nanotubes, buckyballs) in extraterrestrial environments (circumstellar envelopes, planetary nebulae, molecular clouds) and combustion systems. While key studies have been conducted exploiting traditional, high-temperature mechanisms such as the hydrogen abstraction-acetylene addition (HACA) and phenyl addition-dehydrocyclization (PAC) pathways, the complexity of extreme environments highlights the necessity of investigating chemically diverse mass growth reaction mechanisms leading to PAHs. Employing the crossed molecular beams technique coupled with electronic structure calculations, we report on the gas-phase synthesis of phenanthrene (C14H10)-a three-ring, 14π benzenoid PAH-via a phenylethynyl addition-cyclization-aromatization mechanism, featuring bimolecular reactions of the phenylethynyl radical (C6H5CC, X2A1) with benzene (C6H6) under single collision conditions. The dynamics involve a phenylethynyl radical addition to benzene without entrance barrier leading eventually to phenanthrene via indirect scattering dynamics through C14H11 intermediates. The barrierless nature of reaction allows rapid access to phenanthrene in low-temperature environments such as cold molecular clouds which can reach temperatures as low as 10 K. This mechanism constitutes a unique, low-temperature framework for the formation of PAHs as building blocks in molecular mass growth processes to carbonaceous nanostructures in extraterrestrial environments thus affording critical insight into the low-temperature hydrocarbon chemistry in our universe.

Transformation of Mercurous [Hg(I)] Species during Laboratory Standard Preparation and Analysis: Implication for Environmental Analysis.

Hg(I) may control Hg redox kinetics; however, its metastable nature hinders analysis. Herein, the stability of Hg(I) during standard preparation and analysis was studied. Gravimetric analysis showed that Hg(I) was stable in its stock solution (1000 mg L-1), yet completely disproportionated when its dilute solution (10 µg L-1) was analyzed using liquid chromatography (LC)-ICPMS. The Hg(I) dimer can form through an energetically favorable comproportionation between Hg(0) and Hg(II), as supported by density functional theory calculation and traced by the rapid isotope exchange between 199Hg(0)aq and 202Hg(II). However, the separation of Hg(0) and Hg(II) (e.g., LC process) triggered its further disproportionation. Polypropylene container, increasing headspace, decreasing pH, and increasing dissolved oxygen significantly enhanced the disproportionation or redox transformations of Hg(I). Thus, using a glass container without headspace and maintaining a slightly alkaline solution are recommended for the dilute Hg(I) stabilization. Notably, we detected elevated concentrations of Hg(I) (4.4-6.1 µg L-1) in creek waters from a heavily Hg-polluted area, accounting for 54-70% of total dissolved Hg. We also verified the reductive formation of Hg(I) in Hg(II)-spiked environmental water samples, where Hg(I) can stably exist in aquatic environments for at least 24 h, especially in seawater. These findings provide mechanistic insights into the transformation of Hg(I), which are indicative of its further environmental identification.

One Collision-Two Substituents: Gas-Phase Preparation of Xylenes under Single-Collision Conditions.

The fundamental reaction pathways to the simplest dialkylsubstituted aromatics-xylenes (C6 H4 (CH3 )2 )-in high-temperature combustion flames and in low-temperature extraterrestrial environments are still unknown, but critical to understand the chemistry and molecular mass growth processes in these extreme environments. Exploiting crossed molecular beam experiments augmented by state-of-the-art electronic structure and statistical calculations, this study uncovers a previously elusive, facile gas-phase synthesis of xylenes through an isomer-selective reaction of 1-propynyl (methylethynyl, CH3 CC) with 2-methyl-1,3-butadiene (isoprene, C5 H8 ). The reaction dynamics are driven by a barrierless addition of the radical to the diene moiety of 2-methyl-1,3-butadiene followed by extensive isomerization (hydrogen shifts, cyclization) prior to unimolecular decomposition accompanied by aromatization via atomic hydrogen loss. This overall exoergic reaction affords a preparation of xylenes not only in high-temperature environments such as in combustion flames and around circumstellar envelopes of carbon-rich Asymptotic Giant Branch (AGB) stars, but also in low-temperature cold molecular clouds (10 K) and in hydrocarbon-rich atmospheres of planets and their moons such as Triton and Titan. Our study established a hitherto unknown gas-phase route to xylenes and potentially more complex, disubstituted benzenes via a single collision event highlighting the significance of an alkyl-substituted ethynyl-mediated preparation of aromatic molecules in our Universe.

Gas-phase formation of the resonantly stabilized 1-indenyl (C9H7•) radical in the interstellar medium.

The 1-indenyl (C9H7•) radical, a prototype aromatic and resonantly stabilized free radical carrying a six- and a five-membered ring, has emerged as a fundamental molecular building block of nonplanar polycyclic aromatic hydrocarbons (PAHs) and carbonaceous nanostructures in deep space and combustion systems. However, the underlying formation mechanisms have remained elusive. Here, we reveal an unconventional low-temperature gas-phase formation of 1-indenyl via barrierless ring annulation involving reactions of atomic carbon [C(3P)] with styrene (C6H5C2H3) and propargyl (C3H3•) with phenyl (C6H5•). Macroscopic environments like molecular clouds act as natural low-temperature laboratories, where rapid molecular mass growth to 1-indenyl and subsequently complex PAHs involving vinyl side-chained aromatics and aryl radicals can occur. These reactions may account for the formation of PAHs and their derivatives in the interstellar medium and carbonaceous chondrites and could close the gap of timescales of their production and destruction in our carbonaceous universe.

Gas-phase preparation of azulene (C10H8) and naphthalene (C10H8) via the reaction of the resonantly stabilized fulvenallenyl and propargyl radicals.

Synthetic routes to the 10π Hückel aromatic azulene (C10H8) molecule, the simplest polycyclic aromatic hydrocarbon carrying an adjacent five- and seven-membered ring, have been of fundamental importance due to the role of azulene - a structural isomer of naphthalene - as an essential molecular building block of saddle-shaped carbonaceous nanostructures such as curved nanographenes and nanoribbons. Here, we report on the very first gas phase preparation of azulene by probing the gas-phase reaction between two resonantly stabilized radicals, fulvenallenyl and propargyl , in a molecular beam through isomer-resolved vacuum ultraviolet photoionization mass spectrometry. Augmented by electronic structure calculations, the novel Fulvenallenyl Addition Cyclization Aromatization (FACA) reaction mechanism affords a versatile concept for introducing the azulene moiety into polycyclic aromatic systems thus facilitating an understanding of barrierless molecular mass growth processes of saddle-shaped aromatics and eventually carbonaceous nanoparticles (soot, interstellar grains) in our universe.

Gas-Phase Synthesis of Coronene through Stepwise Directed Ring Annulation.

Molecular beam experiments together with electronic structure calculations provide the first evidence of a complex network of elementary gas-phase reactions culminating in the bottom-up preparation of the 24π aromatic coronene (C24H12) molecule─a representative peri-fused polycyclic aromatic hydrocarbon (PAH) central to the complex chemistry of combustion systems and circumstellar envelopes of carbon stars. The gas-phase synthesis of coronene proceeds via aryl radical-mediated ring annulations through benzo[e]pyrene (C20H12) and benzo[ghi]perylene (C22H12) involving armchair-, zigzag-, and arm-zig-edged aromatic intermediates, highlighting the chemical diversity of molecular mass growth processes to polycyclic aromatic hydrocarbons. The isomer-selective identification of five- to six-ringed aromatics culminating with the detection of coronene is accomplished through photoionization and is based upon photoionization efficiency curves along with photoion mass-selected threshold photoelectron spectra, providing a versatile concept of molecular mass growth processes via aromatic and resonantly stabilized free radical intermediates to two-dimensional carbonaceous nanostructures.

Unconventional gas-phase preparation of the prototype polycyclic aromatic hydrocarbon naphthalene (C10H8) via the reaction of benzyl (C7H7) and propargyl (C3H3) radicals coupled with hydrogen-atom assisted isomerization.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the interstellar medium and in meteorites such as Murchison and Allende and signify the missing link between resonantly stabilized free radicals and carbonaceous nanoparticles (soot particles, interstellar grains). However, the predicted lifetime of interstellar PAHs of some 108 years imply that PAHs should not exist in extraterrestrial environments suggesting that key mechanisms of their formation are elusive. Exploiting a microchemical reactor and coupling these data with computational fluid dynamics (CFD) simulations and kinetic modeling, we reveal through an isomer selective product detection that the reaction of the resonantly stabilized benzyl and the propargyl radicals synthesizes the simplest representative of PAHs - the 10π Hückel aromatic naphthalene (C10H8) molecule - via the novel Propargyl Addition-BenzAnnulation (PABA) mechanism. The gas-phase preparation of naphthalene affords a versatile concept of the reaction of combustion and astronomically abundant propargyl radicals with aromatic radicals carrying the radical center at the methylene moiety as a previously passed over source of aromatics in high temperature environments thus bringing us closer to an understanding of the aromatic universe we live in.

Gas phase synthesis of the C40 nano bowl C40H10.

Nanobowls represent vital molecular building blocks of end-capped nanotubes and fullerenes detected in combustion systems and in deep space such as toward the planetary nebula TC-1, but their fundamental formation mechanisms have remained elusive. By merging molecular beam experiments with electronic structure calculations, we reveal a complex chain of reactions initiated through the gas-phase preparation of benzocorannulene (C24H12) via ring annulation of the corannulenyl radical (C20H9•) by vinylacetylene (C4H4) as identified isomer-selectively in situ via photoionization efficiency curves and photoion mass-selected threshold photoelectron spectra. In silico studies provided compelling evidence that the benzannulation mechanism can be expanded to pentabenzocorannulene (C40H20) followed by successive cyclodehydrogenation to the C40 nanobowl (C40H10) - a fundamental building block of buckminsterfullerene (C60). This high-temperature pathway opens up isomer-selective routes to nanobowls via resonantly stabilized free-radical intermediates and ring annulation in circumstellar envelopes of carbon stars and planetary nebulae as their descendants eventually altering our insights of the complex chemistry of carbon in our Galaxy.

Anticancer Drug Doxorubicin Spontaneously Reacts with GTP and dGTP.

Here, we reported a spontaneous reaction between anticancer drug doxorubicin and GTP or dGTP. Incubation of doxorubicin with GTP or dGTP at 37 °C or above yields a covalent product: the doxorubicin-GTP or -dGTP conjugate where a covalent bond is formed between the C14 position of doxorubicin and the 2-amino group of guanine. Density functional theory calculations show the feasibility of this spontaneous reaction. Fluorescence imaging studies demonstrate that the doxorubicin-GTP and -dGTP conjugates cannot enter nuclei although they rapidly accumulate in human SK-OV-3 and NCI/ADR-RES cells. Consequently, the doxorubicin-GTP and -dGTP conjugates are less cytotoxic than doxorubicin. We also demonstrate that doxorubicin binds to ATP, GTP, and other nucleotides with a dissociation constant (Kd) in the sub-millimolar range. Since human cells contain millimolar levels of ATP and GTP, these results suggest that doxorubicin may target ATP and GTP, energy molecules that support essential processes in living organisms.

Gas-phase detection of oxirene.

Oxirenes-highly strained 4π Hückel antiaromatic organics-have been recognized as key reactive intermediates in the Wolff rearrangement and in interstellar environments. Predicting short lifetimes and tendency toward ring opening, oxirenes are one of the most mysterious classes of organic transients, with the isolation of oxirene (c-C2H2O) having remained elusive. Here, we report on the preparation of oxirene in low-temperature methanol-acetaldehyde matrices upon energetic processing through isomerization of ketene (H2CCO) followed by resonant energy transfer of the internal energy of oxirene to the vibrational modes (hydroxyl stretching and bending, methyl deformation) of methanol. Oxirene was detected upon sublimation in the gas phase exploiting soft photoionization coupled with a reflectron time-of-flight mass spectrometry. These findings advance our fundamental understanding of the chemical bonding and stability of cyclic, strained molecules and afford a versatile strategy for the synthesis of highly ring-strained transients in extreme environments.

Exotic Reaction Dynamics in the Gas-Phase Preparation of Anthracene (C14H10) via Spiroaromatic Radical Transients in the Indenyl-Cyclopentadienyl Radical-Radical Reaction.

The gas-phase reaction between the 1-indenyl (C9H7•) radical and the cyclopentadienyl (C5H5•) radical has been investigated for the first time using synchrotron-based mass spectrometry coupled with a pyrolytic reactor. Soft photoionization with tunable vacuum ultraviolet photons afforded for the isomer-selective identification of the production of phenanthrene, anthracene, and benzofulvalene (C14H10). The classical theory prevalent in the literature proposing that radicals combine only at their specific radical centers is challenged by our discovery of an unusual reaction pathway that involves a barrierless combination of a resonantly stabilized hydrocarbon radical with an aromatic radical at the carbon atom adjacent to the traditional C1 radical center; this unconventional addition is followed by substantial isomerization into phenanthrene and anthracene via a category of exotic spiroaromatic intermediates. This result leads to a deeper understanding of the evolution of the cosmic carbon budget and provides new methodologies for the bottom-up synthesis of unique spiroaromatics that may be relevant for the synthesis of more complex aromatic carbon skeletons in deep space.

Unconventional Pathway in the Gas-Phase Synthesis of 9H-Fluorene (C13 H10 ) via the Radical-Radical Reaction of Benzyl (C7 H7 ) with Phenyl (C6 H5 ).

The simplest polycyclic aromatic hydrocarbon (PAH) carrying a five-membered ring-9H-fluorene (C13 H10 )-is produced isomer-specifically in the gas phase by reacting benzyl (C7 H7 ⋅) with phenyl (C6 H5 ⋅) radicals in a pyrolytic reactor coupled with single photon ionization mass spectrometry. The unconventional mechanism of reaction is supported by theoretical calculations, which first produces diphenylmethane and unexpected 1-(6-methylenecyclohexa-2,4-dienyl)benzene intermediates (C13 H12 ) accessed via addition of the phenyl radical to the ortho position of the benzyl radical. These findings offer convincing evidence for molecular mass growth processes defying conventional wisdom that radical-radical reactions are initiated through recombination at their radical centers. The structure of 9H-fluorene acts as a molecular building block for complex curved nanostructures like fullerenes and nanobowls providing fundamental insights into the hydrocarbon evolution in high temperature settings.

On the Mechanism of Soot Nucleation. IV. Molecular Growth of the Flattened E-Bridge.

Rotationally excited dimerization of aromatic moieties, a mechanism proposed recently to explain the initial steps of soot particle inception in combustion and pyrolysis of hydrocarbons, produces a molecular structure, termed E-bridge, combining the two aromatics via five-membered aromatic rings sharing a common bond. The present study investigates a hydrogen-mediated addition of acetylene to the fused five-membered ring part of the E-bridge forming a seven-membered ring. The carried out quantum-mechanical and rate theoretical calculations indicate the plausibility of such capping reactions, and kinetic Monte Carlo simulations demonstrate their frequent occurrence. The capping frequency, however, is limited by "splitting" the fused five-membered bridge due to five-membered ring migration. A similar migration of edge seven-membered rings is shown to be also rapid but short, as their encounter with five-membered rings converts them both into six-membered rings.

Gas-Phase Formation of 1,3,5,7-Cyclooctatetraene (C8H8) through Ring Expansion via the Aromatic 1,3,5-Cyclooctatrien-7-yl Radical (C8H9•) Transient.

Gas-phase 1,3,5,7-cyclooctatetraene (C8H8) and triplet aromatic 1,3,5,7-cyclooctatetraene (C8H8) were formed for the first time through bimolecular methylidyne radical (CH)-1,3,5-cycloheptatriene (C7H8) reactions under single-collision conditions on a doublet surface. The reaction involves methylidyne radical addition to the olefinic π electron system of 1,3,5-cycloheptatriene followed by isomerization and ring expansion to an aromatic 1,3,5-cyclooctatrien-7-yl radical (C8H9•). The chemically activated doublet radical intermediate undergoes unimolecular decomposition to 1,3,5,7-cyclooctatetraene. Substituted 1,3,5,7-cyclooctatetraene molecules can be prepared in the gas phase with hydrogen atom(s) in the 1,3,5-cycloheptatriene reactant being replaced by organic side groups. These findings are also of potential interest to organometallic chemists by expanding the synthesis of exotic transition-metal complexes incorporating substituted 1,3,5,7-cyclooctatetraene dianion (C8H82-) ligands and to untangle the unimolecular decomposition of chemically activated and substituted 1,3,5-cyclooctatrien-7-yl radical, eventually gaining a fundamental insight of their bonding chemistry, electronic structures, and stabilities.

Computational Study of the Gas-Phase Thermal Degradation of Perfluoroalkyl Carboxylic Acids.

Perfluoroalkyl carboxylic acids (PFCAs) are persistent and ubiquitous pollutants. Environmental remediation is often achieved by absorption on matrices followed by high-temperature thermal treatment to desorb and decompose the PFCAs. Detailed product studies of the thermal degradation of PFCAs have been hampered by the complex nature of product mixtures and associated analytical challenges. On the basis of high-level computational studies, we propose reaction pathways and mechanisms for the high-temperature mineralization of a series of linear PFCAs with a backbone length from C-4 to C-8. The favored initial reaction pathways are nonselective C-C bond homolytic cleavages (with bond dissociation energies of ∼75-90 kcal/mol), resulting in carbon-centered radicals which can undergo ß-scissions (Ea ≈ 30-40 kcal/mol) which can be preceded by F atom shifts (Ea ≈ 30-45 kcal/mol). In competing barrierless processes, the carbon-centered radicals can lose •F, resulting in the formation of volatile perfluoroalkenes (ΔH ≈ 50-80 kcal/mol). A variety of competing fragmentation processes yield shorter chain perfluorinated PFCAs, isomeric alkenes, alkenoic acids, alkyl, and alkyloic acid radicals. The results provide the energetics for primary, secondary, and tertiary reaction products and insight into the fundamental understanding of the pyrolytic pathways of PFCAs leading to their mineralization.

Directed gas phase preparation of ethynylallene (H2CCCHCCH; X1A') via the crossed molecular beam reaction of the methylidyne radical (CH; X2Π) with vinylacetylene (H2CCHCCH; X1A').

The gas-phase bimolecular reaction of the methylidyne (CH; X2Π) radical with vinylacetylene (H2CCHCCH; X1A') was conducted at a collision energy of 20.3 kJ mol-1 under single collision conditions exploiting the crossed molecular beam experimental results merged with ab initio electronic structure calculations and ab initio molecular dynamics (AIMD) simulations. The laboratory data reveal that the bimolecular reaction proceeds barrierlessly via indirect scattering dynamics through long-lived C5H5 reaction intermediate(s) ultimately dissociating to C5H4 isomers along with atomic hydrogen with the latter predominantly originating from the vinylacetylene reactant as confirmed by the isotopic substitution experiments in the D1-methylidyne-vinylacetylene reaction. Combined with ab initio calculations of the potential energy surface (PES) and statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations, the experimental determined reaction energy of -146 ± 26 kJ mol-1 along with the distribution minimum of T(θ) at 90° and isotopic substitution experiments suggest ethynylallene (p1; ΔrG = -230 ± 4 kJ mol-1) as the dominant product. The ethynylallene (p1) may be formed with extensive rovibrational excitation, which would result in a lower maximum translational energy. Further, AIMD simulations reveal that the reaction dynamics leads to p1 (ethynylallene, 75%) plus atomic hydrogen with the dominant initial complex being i1 formed by methylidyne radical addition to the double CC bond in vinylacetylene. Overall, combining the crossed molecular beam experimental results with ab initio electronic structure calculations and ab initio molecular dynamics (AIMD) simulations, ethynylallene (p1) is expected to represent the dominant product in the reaction of the methylidyne (CH; X2Π) radical with vinylacetylene (H2CCHCCH; X1A').

Gas-phase synthesis of racemic helicenes and their potential role in the enantiomeric enrichment of sugars and amino acids in meteorites.

The molecular origins of homochirality on Earth is not understood well, particularly how enantiomerically enriched molecules of astrobiological significance like sugars and amino acids might have been synthesized on icy grains in space preceding their delivery to Earth. Polycyclic aromatic hydrocarbons (PAHs) identified in carbonaceous chondrites could have been processed in molecular clouds by circularly polarized light prior to the depletion of enantiomerically enriched helicenes onto carbonaceous grains resulting in chiral islands. However, the fundamental low temperature reaction mechanisms leading to racemic helicenes are still unknown. Here, by exploiting synchrotron based molecular beam photoionization mass spectrometry combined with electronic structure calculations, we provide compelling testimony on barrierless, low temperature pathways leading to racemates of [5] and [6]helicene. Astrochemical modeling advocates that gas-phase reactions in molecular clouds lead to racemates of helicenes suggesting a pathway for future astronomical observation and providing a fundamental understanding for the origin of homochirality on early Earth.

Gas-Phase Preparation of Subvalent Germanium Monoxide (GeO, X1Σ+) via Non-Adiabatic Reaction Dynamics in the Exit Channel.

The subvalent germanium monoxide (GeO, X1Σ+) molecule has been prepared via the elementary reaction of atomic germanium (Ge, 3Pj) and molecular oxygen (O2, X3Σg-) with each reactant in its electronic ground state by means of single-collision conditions. The merging of electronic structure calculations with crossed beam experiments suggests that the formation of germanium monoxide (GeO, X1Σ+) commences on the singlet surface through unimolecular decomposition of a linear singlet collision complex (GeOO, i1, C∞v, 1Σ+) via intersystem crossing (ISC) yielding nearly exclusively germanium monoxide (GeO, X1Σ+) along with atomic oxygen in its electronic ground state [p1, O(3P)]. These results provide a sophisticated reaction mechanism of the germanium-oxygen system and demonstrate the efficient "heavy atom effect" of germanium in ISC yielding (nearly) exclusive singlet germanium monoxide and triplet atomic oxygen compared to similar systems (carbon dioxide and dinitrogen monoxide), in which non-adiabatic reaction dynamics represent only minor channels.

Gas-Phase Study of the Elementary Reaction of the D1-Ethynyl Radical (C2D; X2Σ+) with Propylene (C3H6; X1A') under Single-Collision Conditions.

The bimolecular gas-phase reactions of the D1-ethynyl radical (C2D; X2Σ+) with propylene (C3H6; X1A') and partially substituted D3-3,3,3-propylene (C2H3CD3; X1A') were studied under single collision conditions utilizing the crossed molecular beams technique. Combining our laboratory data with electronic structure and statistical calculations, the D1-ethynyl radical is found to add without barrier to the C1 and C2 carbons of the propylene reactant, resulting in doublet C5H6D intermediate(s) with lifetime(s) longer than their rotational period(s). These intermediates undergo isomerization and unimolecular decomposition via atomic hydrogen loss through tight exit transition states forming predominantly cis/trans-3-penten-1-yne ((HCC)CH═CH(CH3)) and, to a minor amount, 3-methyl-3-buten-1-yne ((HCC)C(CH3)═CH2) via overall exoergic reactions. Although the title reaction does not lead to the cyclopentadiene molecule (c-C5H6, X1A1), high-temperature environments can convert the identified acyclic C5H6 isomers through hydrogen atom assisted isomerization to cyclopentadiene (c-C5H6, X1A1). Since both the ethynyl radical and propylene reactants have been observed in cold interstellar environments such as TMC-1 and the reaction is exoergic and all barriers lie below the energy of the separated reactants, these C5H6 product isomers are predicted to form in those low-temperature regions.