Photochemically triggered cheletropic formation of cyclopropenone (c-C<sub>3</sub>H<sub>2</sub>O) from carbon monoxide and electronically excited acetylene

Wang, Jia; Kleimeier, N. Fabian; Johnson, Rebecca N.; Gozem, Samer; Abplanalp, Matthew J.; Turner, Andrew M.; Marks, Joshua H.; Kaiser, Ralf I.

doi:10.1039/d2cp01978g

Cited by 4 publications

(3 citation statements)

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“…PI-ReToF-MS is exploited to understand the formation pathways of complex organic molecules (COMs) within interstellar analogue ices. , This technique is utilized here to identify individual CH 2 SO isomers formed in irradiated CO–H 2 S ice based on their ionization energies. The PI-ReToF-MS data of the photoionized, desorbing molecules from the irradiated ices are compiled in Figure ; these raw data are required to extract TPD profiles of m/z = 62 at two photon energies of 10.82 and 10.39 eV (Figure a).…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2022

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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 (H 2 S) at 5 K. Utilizing single photoionization reflectron timeof-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.

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Section: Resultsmentioning

confidence: 99%

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

et al. 2022

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“…The simplest one among these, cyclopropenylidene (CPD), ubiquitous in the ISM, − has been recently explored theoretically to appraise its cooperativity, in terms of its tendency toward the formation of homologous molecular clusters and also with water . Cyclopropenone (HCCOCH, or c-C 3 H 2 O, herein abbreviated “CPN”), − is another simple exotic carbene that possesses an intrinsic C 2v symmetry, which manifests in the Sagittarius B2 ( N ) region of the ISM. CPN has been theoretically, as well as experimentally investigated upon, along with its derivatives, over the past seven decades. − In particular, CPN plays its role as a tracer in nonequilibrium chemistry when interstellar acetylene and carbon-monoxide ices react under a cosmic shower .…”

Section: Introductionmentioning

confidence: 99%

Theoretical Appraisal of Cyclopropenone: Aggregation and Complexes with Water

et al. 2023

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Cyclopropenone (HCCOCH, “CPN”) is an exotic quasi-aromatic cyclic carbene that abounds in the interstellar medium (ISM). Astronomical observations suggest that (i) stagnate CPN exhibits a tendency to polymerize and that (ii) interactions may occur between CPN and water that is also ubiquitous in the ISM. In this light, density functional theory investigations reveal cooperative hydrogen bonding, which leads to stable polymeric conformations of (CPN) n , tracked up to n = 14. Stable agglomerations with water, however, constitute at best only two CPN and two water molecules, signifying that while CPN exhibits remarkable cooperativity for “cohesive” clustering via hydrogen bonding, this tendency is markedly diminished for “hetero”-interactions. Multifaceted data are employed to probe cogent molecular descriptors, such as structure and energetics of various conformers, vibrational spectroscopic response, molecular electrostatic potential (MESP), effective atomic charges: all these, in unison, describe the evolution of the characteristics upon cluster formation. Salient stretching frequency shifts, as well as charge redistribution gleaned from MESP morphology, have a direct bearing on variegated hydrogen bonding patterns: linear, nonlinear, as well as bifurcated. In particular, characteristic C–H, CO stretching, and O–H vibrations in the water complexes reveal a “softening” (downshift) of frequencies. While small conformers have markedly distinct MESP variations, the differences become less pronounced with incremental clustering, an effect substantiated by corresponding emergent atomic charges.

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“…It is worth noting that the formation of 1 may involve the excited state photochemistry of low-lying electronic states of acetylene, which can be accessed by the kinetic energy of the impinging electrons during the irradiation. Recent studies have shown that excited states of acetylene play key roles in the formation of cyclopropenone ( c -C 3 H 2 O) and benzene (C 6 H 6 ) in interstellar acetylene-containing analog ices. ,, The excited acetylene molecule may react with the nearby acetylene molecule to form 1 via a concerted mechanism in low-temperature ices. The second pathway for the formation of 1 may involve vinylacetylene ( 7 ), which undergoes isomerization to form 1 via a barrier of 203 kJ mol –1 and a reaction energy of 140 kJ mol –1 .…”

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Bottom-Up Formation of Antiaromatic Cyclobutadiene (c-C₄H₄) in Interstellar Ice Analogs

Wang,

Marks,

Eckhardt

et al. 2024

J. Phys. Chem. Lett.

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Antiaromatic cyclobutadiene (c-C 4 H 4 ) is the simplest prototype of [n]annulenes and a key reactive intermediate with significant ring strain, serving as the model compound for antiaromatic systems in organic chemistry. Here, we report the first bottom-up formation of cyclobutadiene in low-temperature acetylene (C 2 H 2 ) ices exposed to energetic electrons. Cyclobutadiene was isolated and detected in the gas phase upon sublimation utilizing vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry along with ultraviolet photolysis studies. These findings advance our fundamental understanding of the exotic chemistry and preparation of highly strained antiaromatic cycles through nonequilibrium chemistry in interstellar environments, thus affording a possible route for the formation of highly strained molecules such as the hitherto elusive tetrahedrane (C 4 H 4 ). Because acetylene is a major product of the photolysis and radiolysis of methane (CH 4 ) ice, an abundant component of interstellar ices, our results suggest that cyclobutadiene can likely be formed in methane-rich ices of cold molecular clouds.

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Photochemically triggered cheletropic formation of cyclopropenone (c-C₃H₂O) from carbon monoxide and electronically excited acetylene

Abstract: Cyclopropenone is one of few organic molecules detected in interstellar molecular clouds to date. Its formation mechanism from carbon monoxide and photoexcited acetylene is investigated, giving key insight into its formation in extreme conditions.

Cited by 4 publications

References 70 publications

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

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

Theoretical Appraisal of Cyclopropenone: Aggregation and Complexes with Water

Bottom-Up Formation of Antiaromatic Cyclobutadiene (c-C₄H₄) in Interstellar Ice Analogs

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Photochemically triggered cheletropic formation of cyclopropenone (c-C3H2O) from carbon monoxide and electronically excited acetylene

Abstract: Cyclopropenone is one of few organic molecules detected in interstellar molecular clouds to date. Its formation mechanism from carbon monoxide and photoexcited acetylene is investigated, giving key insight into its formation in extreme conditions.

Cited by 4 publications

References 70 publications

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

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

Theoretical Appraisal of Cyclopropenone: Aggregation and Complexes with Water

Bottom-Up Formation of Antiaromatic Cyclobutadiene (c-C4H4) in Interstellar Ice Analogs

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Photochemically triggered cheletropic formation of cyclopropenone (c-C₃H₂O) from carbon monoxide and electronically excited acetylene

Bottom-Up Formation of Antiaromatic Cyclobutadiene (c-C₄H₄) in Interstellar Ice Analogs