Synthesis of interstellar propen-2-ol (CH3C(OH)CH2) - the simplest enol tautomer of a ketone.

Enols - tautomers of ketones or aldehydes - are anticipated to be ubiquitous in the interstellar medium and play a key role in the formation of complex organic molecules in deep space, but their fundamental formation mechanisms have remained largely elusive as of now. Here we present a combined experimental and computational study demonstrating the first preparation of propen-2-ol (CH3C(OH)CH2) and its isomer methyl vinyl ether (CH3OCHCH2) in low-temperature acetone (CH3COCH3) ices upon exposure to energetic electrons. Propen-2-ol is the simplest enol tautomer of a ketone. Exploiting tunable vacuum ultraviolet photoionization in conjunction with reflectron time-of-flight mass spectrometry, propen-2-ol and methyl vinyl ether were monitored in the gas phase upon sublimation during the temperature-programmed desorption process suggesting that both isomers are promising candidates for future astronomical searches such as via the James Webb Space Telescope. Electronic structure calculations reveal that the barrier of keto-enol tautomerization can be reduced by more than a factor of two (162 kJ mol-1) through the involvement of solvating water molecules under realistic conditions on interstellar grains. The implicit solvent effects, i.e., the influences of the solvent dipole field on the barrier height are found to be minimal and do not exceed 10 kJ mol-1. Our findings signify a crucial step toward a better understanding of the enolization of ketones in the interstellar medium thus constraining the molecular structures and complexity of molecules that form in extraterrestrial ices - ketones - through non-equilibrium chemistry.

Exploring the Chemical Dynamics of Phenylethynyl Radical (C6H5CC; X2A1) Reactions with Allene (H2CCCH2; X1A1) and Methylacetylene (CH3CCH; X1A1).

The bimolecular gas-phase reactions of the phenylethynyl radical (C6H5CC, X2A1) with allene (H2CCCH2), allene-d4 (D2CCCD2), and methylacetylene (CH3CCH) were studied under single-collision conditions utilizing the crossed molecular beams technique and merged with electronic structure and statistical calculations. The phenylethynyl radical was found to add without an entrance barrier to the C1 carbon of the allene and methylacetylene reactants, resulting in doublet C11H9 collision complexes with lifetimes longer than their rotational periods. These intermediates underwent unimolecular decomposition via atomic hydrogen loss through tight exit transition states in facile radical addition─hydrogen atom elimination mechanisms forming predominantly 3,4-pentadien-1-yn-1-ylbenzene (C6H5CCCHCCH2) and 1-phenyl-1,3-pentadiyne (C6H5CCCCCH3) in overall exoergic reactions (-110 kJ mol-1 and -130 kJ mol-1) for the phenylethynyl-allene and phenylethynyl-methylacetylene systems, respectively. These barrierless reaction mechanisms mirror those of the ethynyl radical (C2H, X2Σ+) with allene and methylacetylene forming predominantly ethynylallene (HCCCHCCH2) and methyldiacetylene (HCCCCCH3), respectively, suggesting that in the aforementioned reactions the phenyl group acts as a spectator. These molecular mass growth processes are accessible in low-temperature environments such as cold molecular clouds (TMC-1) or Saturn's moon Titan, efficiently incorporating a benzene ring into unsaturated hydrocarbons.

The Reaction of o-Benzyne with Vinylacetylene: An Unexplored Way to Produce Naphthalene.

The mechanism and kinetics of the reaction of ortho-benzyne with vinylacetylene have been studied by ab initio and density functional CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) calculations of the pertinent potential energy surface combined with Rice-Ramsperger-Kassel-Marcus - Master Equation calculations of reaction rate constants at various temperatures and pressures. Under prevailing combustion conditions, the reaction has been shown to predominantly proceed by the biradical acetylenic mechanism initiated by the addition of C4 H4 to one of the C atoms of the triple bond in ortho-benzyne by the acetylenic end, with a significant contribution of the concerted addition mechanism. Following the initial reaction steps, an extra six-membered ring is produced and the rearrangement of H atoms in this new ring leads to the formation of naphthalene, which can further dissociate to 1- or 2-naphthyl radicals. The o-C6 H4 +C4 H4 reaction is highly exothermic, by ∼143 kcal/mol to form naphthalene and by 31-32 kcal mol-1 to produce naphthyl radicals plus H, but features relatively high entrance barriers of 9-11 kcal mol-1 . Although the reaction is rather slow, much slower than the reaction of phenyl radical with vinylacetylene, it forms naphthalene and 1- and 2-naphthyl radicals directly, with their relative yields controlled by the temperature and pressure, and thus represents a viable source of the naphthalene core under conditions where ortho-benzyne and vinylacetylene are available.

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.

Formation of Thioformic Acid (HCOSH)─The Simplest Thioacid─in Interstellar Ice Analogues.

Since the observation of the first sulfur-containing molecule, carbon monosulfide (CS), in the interstellar medium (ISM) half a century ago, sulfur-bearing species have attracted great attention from the astrochemistry, astrobiology, and planetary geology communities. Nevertheless, it is still not clear in which forms most of the sulfur resides in molecular clouds, an unsolved problem referred to as "sulfur depletion". Reported herein is the formation of thioformic acid (HCOSH)─the simplest thioacid─in interstellar ice analogues containing carbon monoxide (CO) and hydrogen sulfide (H2S) at 5 K. Utilizing single photoionization reflectron time-of-flight mass spectrometry and isotopically labeled molecules, thioformic acid molecules were selectively photoionized in the temperature-programmed desorption phase. These studies unravel a key reaction pathway to thioformic acid, an organic molecule recently detected toward the giant molecular cloud G+0.693-0.027 and the hot core G31.41+0.31, thus shedding light on interstellar sulfur chemistry.

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.

Directed Gas-Phase Formation of Aminosilylene (HSiNH2; X1A'): The Simplest Silicon Analogue of an Aminocarbene, under Single-Collision Conditions.

The aminosilylene molecule (HSiNH2, X1A')-the simplest representative of an unsaturated nitrogen-silylene-has been formed under single collision conditions via the gas phase elementary reaction involving the silylidyne radical (SiH) and ammonia (NH3). The reaction is initiated by the barrierless addition of the silylidyne radical to the nonbonding electron pair of nitrogen forming an HSiNH3 collision complex, which then undergoes unimolecular decomposition to aminosilylene (HSiNH2) via atomic hydrogen loss from the nitrogen atom. Compared to the isovalent aminomethylene carbene (HCNH2, X1A'), by replacing a single carbon atom with silicon, a profound effect on the stability and chemical bonding of the isovalent methanimine (H2CNH)-aminomethylene (HNCH2) and aminosilylene (HSiNH2)-silanimine (H2SiNH) isomer pairs is shown; i.e., thermodynamical stabilities of the carbene versus silylene are reversed by 220 kJ mol-1. Hence, the isovalency of the main group XIV element silicon was found to exhibit little similarities with the atomic carbon revealing a remarkable effect not only on the reactivity but also on the thermochemistry and chemical bonding.

Directed Gas Phase Formation of the Elusive Silylgermylidyne Radical (H3 SiGe, X2 A'').

The previously unknown silylgermylidyne radical (H3 SiGe; X2 A'') was prepared via the bimolecular gas phase reaction of ground state silylidyne radicals (SiH; X2 Π) with germane (GeH4 ; X1 A1 ) under single collision conditions in crossed molecular beams experiments. This reaction begins with the formation of a van der Waals complex followed by insertion of silylidyne into a germanium-hydrogen bond forming the germylsilyl radical (H3 GeSiH2 ). A hydrogen migration isomerizes this intermediate to the silylgermyl radical (H2 GeSiH3 ), which undergoes a hydrogen shift to an exotic, hydrogen-bridged germylidynesilane intermediate (H3 Si(µ-H)GeH); this species emits molecular hydrogen forming the silylgermylidyne radical (H3 SiGe). Our study offers a remarkable glance at the complex reaction dynamics and inherent isomerization processes of the silicon-germanium system, which are quite distinct from those of the isovalent hydrocarbon system (ethyl radical; C2 H5 ) eventually affording detailed insights into an exotic chemistry and intriguing chemical bonding of silicon-germanium species at the microscopic level exploiting crossed molecular beams.

Combined Crossed Molecular Beams and Ab Initio Study of the Bimolecular Reaction of Ground State Atomic Silicon (Si; 3 P) with Germane (GeH4 ; X1 A1 ).

The chemical dynamics of the elementary reaction of ground state atomic silicon (Si; 3 P) with germane (GeH4 ; X1 A1 ) were unraveled in the gas phase under single collision condition at a collision energy of 11.8±0.3 kJ mol-1 exploiting the crossed molecular beams technique contemplated with electronic structure calculations. The reaction follows indirect scattering dynamics and is initiated through an initial barrierless insertion of the silicon atom into one of the four chemically equivalent germanium-hydrogen bonds forming a triplet collision complex (HSiGeH3 ; 3 i1). This intermediate underwent facile intersystem crossing (ISC) to the singlet surface (HSiGeH3 ; 1 i1). The latter isomerized via at least three hydrogen atom migrations involving exotic, hydrogen bridged reaction intermediates eventually leading to the H3 SiGeH isomer i5. This intermediate could undergo unimolecular decomposition yielding the dibridged butterfly-structured isomer 1 p1 (Si(µ-H2 )Ge) plus molecular hydrogen through a tight exit transition state. Alternatively, up to two subsequent hydrogen shifts to i6 and i7, followed by fragmentation of each of these intermediates, could also form 1 p1 (Si(µ-H2 )Ge) along with molecular hydrogen. The overall non-adiabatic reaction dynamics provide evidence on the existence of exotic dinuclear hydrides of main group XIV elements, whose carbon analog structures do not exist.

Mechanism and kinetics of the oxidation of 1,3-butadien-1-yl (n-C4H5): a theoretical study.

Ab initio CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) calculations of the C4H5O2 potential energy surface have been combined with Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) calculations of temperature- and pressure-dependent rate constants and product branching ratios to unravel the mechanism and kinetics of the n-C4H5 + O2 reaction. The results indicate that the reaction is fast, with the total rate constant being in the range of 3.4-5.6 × 10-11 cm3 molecule-1 s-1. The main products include 1-oxo-n-butadienyl + O and acrolein + HCO, with their cumulative yield exceeding 90% at temperatures above 1500 K. Two conformers of 1-oxo-n-butadienyl + O are formed via a simple mechanism of O2 addition to the radical site of n-C4H5 followed by the cleavage of the O-O bond proceeding via a van der Waals C4H5OO complex. Alternatively, the pathways leading to acrolein + HCO involve significant reorganization of the heavy-atom skeleton either via formal migration of one O atom to the opposite end of the molecule or its insertion into the C1-C2 bond. Not counting thermal stabilization of the initial peroxy adducts, which prevails at low temperatures and high pressures, all other products share a minor yield of under 5%. Rate constants for the significant reaction channels have been fitted to modified Arrhenius expressions and are proposed for kinetic modeling of the oxidation of aromatic molecules and 1,3-butadiene. As a secondary reaction, n-C4H5 + O2 can be a source for the formation of acrolein observed experimentally in oxidation of the phenyl radical at low combustion temperatures, whereas another significant (secondary) product of the C6H5 + O2 reaction, furan, could be formed through unimolecular decomposition of 1-oxo-n-butadienyl. Both the n-C4H5 + O2 reaction and unimolecular decomposition of its 1-oxo-n-butadienyl primary product are shown not to be a substantial source of ketene.

A chemical dynamics study of the reaction of the methylidyne radical (CH, X2Π) with dimethylacetylene (CH3CCCH3, X1A1g).

The gas-phase reaction of the methylidyne (CH; X2Π) radical with dimethylacetylene (CH3CCCH3; X1A1g) was studied at a collision energy of 20.6 kJ mol-1 under single collision conditions with experimental results merged with ab initio calculations of the potential energy surface (PES) and ab initio molecule dynamics (AIMD) simulations. The crossed molecular beam experiment reveals that the reaction proceeds barrierless via indirect scattering dynamics through long-lived C5H7 reaction intermediate(s) ultimately dissociating to C5H6 isomers along with atomic hydrogen with atomic hydrogen predominantly released from the methyl groups as verified by replacing the methylidyne with the D1-methylidyne reactant. AIMD simulations reveal that the reaction dynamics are statistical leading predominantly to p28 (1-methyl-3-methylenecyclopropene, 13%) and p8 (1-penten-3-yne, 81%) plus atomic hydrogen with a significant amount of available energy being channeled into the internal excitation of the polyatomic reaction products. The dynamics are controlled by addition to the carbon-carbon triple bond with the reaction intermediates eventually eliminating a hydrogen atom from the methyl groups of the dimethylacetylene reactant forming 1-methyl-3-methylenecyclopropene (p28). The dominating pathways reveal an unexpected insertion of methylidyne into one of the six carbon-hydrogen single bonds of the methyl groups of dimethylacetylene leading to the acyclic intermediate, which then decomposes to 1-penten-3-yne (p8). Therefore, the methyl groups of dimethylacetylene effectively 'screen' the carbon-carbon triple bond from being attacked by addition thus directing the dynamics to an insertion process as seen exclusively in the reaction of methylidyne with ethane (C2H6) forming propylene (CH3C2H3). Therefore, driven by the screening of the triple bond, one propynyl moiety (CH3CC) acts in four out of five trajectories as a spectator thus driving an unexpected, but dominating chemistry in analogy to the methylidyne - ethane system.

A molecular beam and computational study on the barrierless gas phase formation of (iso)quinoline in low temperature extraterrestrial environments.

Despite remarkable progress toward the understanding of the formation pathways leading to polycyclic aromatic hydrocarbons (PAHs) in combustion systems and in deep space, the complex reaction pathways leading to nitrogen-substituted PAHs (NPAHs) at low temperatures of molecular clouds and hydrocarbon-rich, nitrogen-containing atmospheres of planets and their moons like Titan have remained largely obscure. Here, we demonstrate through laboratory experiments and computations that the simplest prototype of NPAHs - quinoline and isoquinoline (C9H7N) - can be synthesized via rapid and de-facto barrier-less reactions involving o-, m- and p-pyridinyl radicals (C5H4N˙) with vinylacetylene (C4H4) under low-temperature conditions.

Gas-phase synthesis of corannulene - a molecular building block of fullerenes.

Fullerenes (C60, C70) detected in planetary nebulae and carbonaceous chondrites have been implicated to play a key role in the astrochemical evolution of the interstellar medium. However, the formation mechanism of even their simplest molecular building block-the corannulene molecule (C20H10)-has remained elusive. Here we demonstrate via a combined molecular beams and ab initio investigation that corannulene can be synthesized in the gas phase through the reactions of 7-fluoranthenyl (C16H9˙) and benzo[ghi]fluoranthen-5-yl (C18H9˙) radicals with acetylene (C2H2) mimicking conditions in carbon-rich circumstellar envelopes. This reaction sequence reveals a reaction class in which a polycyclic aromatic hydrocarbon (PAH) radical undergoes ring expansion while simultaneously forming an out-of-plane carbon backbone central to 3D nanostructures such as buckybowls and buckyballs. These fundamental reaction mechanisms are critical in facilitating an intimate understanding of the origin and evolution of the molecular universe and, in particular, of carbon in our galaxy.

Theoretical Study of the Phenoxy Radical Recombination with the O(3P) Atom, Phenyl plus Molecular Oxygen Revisited.

Quantum chemical calculations of the C6H5O2 potential energy surface (PES) were carried out to study the mechanism of the phenoxy + O(3P) and phenyl + O2 reactions. CASPT2(15e,13o)/CBS//CASSCF(15e,13o)/DZP multireference calculations were utilized to map out the minimum energy path for the entrance channels of the phenoxy + O(3P) reaction. Stationary points on the C6H5O2 PES were explored at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311++G** level for the species with a single-reference character of the wave function and at the CASPT2(15e,13o)/CBS//B3LYP/6-311++G** level of theory for the species with a multireference character of the wave function. Conventional, variational, and variable reaction coordinate transition-state theories were employed in Rice-Ramsperger-Kassel-Marcus master equation calculations to assess temperature- and pressure-dependent phenomenological rate constants and product branching ratios. The main bimolecular product channels of the phenoxy + O(3P) reaction are concluded to be para/ortho-benzoquinone + H, 2,4-cyclopentadienone + HCO and, at high temperatures, also phenyl + O2. The main bimolecular product channels of the phenyl + O2 reaction include 2,4-cyclopentadienone + HCO at lower temperatures and phenoxy + O(3P) at higher temperatures. For both the phenoxy + O(3P) and phenyl + O2 reactions, the collisional stabilization of peroxybenzene at low temperatures and high pressures competes with the bimolecular product channels.

Theoretical Study of the Reaction of the Methylidyne Radical (CH; X2Π) with 1-Butyne (CH3CH2CCH; X1A').

Ab initio CCSD(T)-F12/cc-pVTZ-f12//ωB97X-D/6-311G(d,p) + ZPE[ωB97X-D/6-311G(d,p)] calculations were carried out to unravel the area of the C5H7 potential energy surface accessed by the reaction of the methylidyne radical with 1-butyne. The results were utilized in Rice-Ramsperger-Kassel-Marcus calculations of the product branching ratios at the zero pressure limit. The preferable reaction mechanism has been shown to involve (nearly) instantaneous decomposition of the initial reaction adducts, whose structures are controlled by the isomeric form of the C4H6 reactant. If CH adds to the triple C≡C bond in the entrance reaction channel, the reaction is predicted to predominantly form the methylenecyclopropene + methyl (CH3) and cyclopropenylidene + ethyl (C2H5) products roughly in a 2:1 ratio. CH insertion into a C-H bond in the methyl group of 1-butyne is anticipated to preferentially form ethylene + propargyl (C3H3) by the C-C bond ß-scission in the initial complex, whereas CH insertion into C-H of the CH2 group would predominantly produce vinylacetylene + methyl (CH3) also by the C-C bond ß-scission in the adduct. The barrierless and highly exoergic CH + 1-butyne reaction, facile in cold molecular clouds, is not likely to lead to the carbon skeleton molecular growth but generates C4H4 isomers methylenecyclopropene, vinylacetylene, and 1,2,3-butatriene and smaller C2 and C3 hydrocarbons such as methyl, ethyl, and propargyl radicals, ethylene, and cyclopropenylidene.

Gas-Phase Formation of C5H6 Isomers via the Crossed Molecular Beam Reaction of the Methylidyne Radical (CH; X2Π) with 1,2-Butadiene (CH3CHCCH2; X1A').

The bimolecular gas-phase reaction of the methylidyne radical (CH; X2Π) with 1,2-butadiene (CH2CCHCH3; X1A') was investigated at a collision energy of 20.6 kJ mol-1 under single collision conditions. Combining our laboratory data with high-level electronic structure calculations, we reveal that this bimolecular reaction proceeds through the barrierless addition of the methylidyne radical to the carbon-carbon double bonds of 1,2-butadiene leading to doublet C5H7 intermediates. These collision adducts undergo a nonstatistical unimolecular decomposition through atomic hydrogen elimination to at least the cyclic 1-vinyl-cyclopropene (p5/p26), 1-methyl-3-methylenecyclopropene (p28), and 1,2-bis(methylene)cyclopropane (p29) in overall exoergic reactions. The barrierless nature of this bimolecular reaction suggests that these cyclic C5H6 isomers might be viable targets to be searched for in cold molecular clouds like TMC-1.

Ozone destruction due to the recombination of oxygen atoms.

Kinetics of ozone destruction due to the recombination of oxygen atoms produced by pulsed 266 nm laser photolysis of O3/M (M = CO2 and/or N2) mixtures was studied using the absorption and emission spectroscopy to follow time evolutions of O3 and electronically excited molecules O2* formed in the recombination process 2O(3P) + M → O2* + M. An unexpected high ozone destruction rate was observed when O2* was present in the system. The kinetic model developed for the oxygen nightglow on the terrestrial planets was adapted to interpret the detected temporal profiles of the ozone number density and the O2* emission intensities. It was deduced that the vibrationally excited singlet delta oxygen molecule O2(a1Δ, υ) formed in the secondary processes reacts efficiently with ozone in the process O2(a1Δ, υ ≥ 3) + O3 → 2O2 + O, and the rate constant of this process was estimated to be 3 × 10-11 cm3 s-1. Ab initio calculations at the CASPT2(14, 12)/cc-pVTZ/UωB97XD/cc-pVTZ level of theory were applied to find the reaction pathway from the reactants to products on the O5 potential energy surface. These calculations revealed that the O2(a1Δ) + O3 reaction is likely to proceed via singlet-triplet intersystem crossing exhibiting an energy barrier of 9.6 kcal/mol, which lies between two and three quanta of vibrational excitation of O2(a1Δ), and hence, O2(a1Δ, υ) with υ ≥ 3 could rapidly react with ozone.

Directed Gas Phase Formation of Silene (H2 SiCH2 ).

The silene molecule (H2 SiCH2 ; X1 A1 ) has been synthesized under single collision conditions via the bimolecular gas phase reaction of ground state methylidyne radicals (CH) with silane (SiH4 ). Exploiting crossed molecular beams experiments augmented by high-level electronic structure calculations, the elementary reaction commenced on the doublet surface through a barrierless insertion of the methylidyne radical into a silicon-hydrogen bond forming the silylmethyl (CH2 SiH3 ; X2 A') complex followed by hydrogen migration to the methylsilyl radical (SiH2 CH3 ; X2 A'). Both silylmethyl and methylsilyl intermediates undergo unimolecular hydrogen loss to silene (H2 SiCH2 ; X1 A1 ). The exploration of the elementary reaction of methylidyne with silane delivers a unique view at the widely uncharted reaction dynamics and isomerization processes of the carbon-silicon system in the gas phase, which are noticeably different from those of the isovalent carbon system thus contributing to our knowledge on carbon silicon bond couplings at the molecular level.

Gas Phase Formation of Methylgermylene (HGeCH3).

The methylgermylene species (HGeCH3 ; X1 A') has been synthesized via the bimolecular gas phase reaction of ground state methylidyne radicals (CH) with germane (GeH4 ) under single collision conditions in crossed molecular beams experiments. Augmented by electronic structure calculations, this elementary reaction was found to proceed through barrierless insertion of the methylidyne radical in one of the four germanium-hydrogen bonds on the doublet potential energy surface yielding the germylmethyl (CH2 GeH3 ; X2 A') collision complex. This insertion is followed by a hydrogen shift from germanium to carbon and unimolecular decomposition of the methylgermyl (GeH2 CH3 ; X2 A') intermediate by atomic hydrogen elimination leading to singlet methylgermylene (HGeCH3 ; X1 A'). Our investigation provides a glimpse at the largely unknown reaction dynamics and isomerization processes of the carbon-germanium system, which are quite distinct from those of the isovalent carbon system thus providing insights into the intriguing chemical bonding of organo germanium species on the most fundamental, microscopic level.

Gas-Phase Synthesis of 3-Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X2 Π) with 1,3-Butadiene (CH2 CHCHCH2 ; X1 Ag ).

The crossed molecular beam reactions of the methylidyne radical (CH; X2 Π) with 1,3-butadiene (CH2 CHCHCH2 ; X1 Ag ) along with their (partially) deuterated counterparts were performed at collision energies of 20.8 kJ mol-1 under single collision conditions. Combining our laboratory data with ab initio calculations, we reveal that the methylidyne radical may add barrierlessly to the terminal carbon atom and/or carbon-carbon double bond of 1,3-butadiene, leading to doublet C5 H7 intermediates with life times longer than the rotation periods. These collision complexes undergo non-statistical unimolecular decomposition through hydrogen atom emission yielding the cyclic cis- and trans-3-vinyl-cyclopropene products with reaction exoergicities of 119±42 kJ mol-1 . Since this reaction is barrierless, exoergic, and all transition states are located below the energy of the separated reactants, these cyclic C5 H6 products are predicted to be accessed even in low-temperature environments, such as in hydrocarbon-rich atmospheres of planets and cold molecular clouds such as TMC-1.