Tricarbon monoxide

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Tricarbon monoxide
Tricarbon-monoxide-2D.svg
Tricarbon-monoxide-3D-vdW.png
Names
Preferred IUPAC name
3-Oxopropa-1,2-dien-1-ylidene
Other names
3-Oxopropadienylidene
Identifiers
3D model (JSmol)
PubChem CID
  • InChI=1S/C3O/c1-2-3-4
    Key: ZCNKODXATWVMAO-UHFFFAOYSA-N
  • [C-]#CC#[O+]
Properties
C3O
Molar mass 52.032 g·mol−1
AppearanceGas
Related compounds
Related oxides
 carbon monoxide
dicarbon monoxide
tetracarbon monoxide
Related compounds
 tricarbon monosulfide
carbon subnitride
HCCCO [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Tricarbon monoxide C3O is a reactive radical oxocarbon molecule found in space, and which can be made as a transient substance in the laboratory. It can be trapped in an inert gas matrix or made as a short lived gas. C3O can be classified as a ketene or an oxocumulene a kind of heterocumulene. [3]

Contents

Natural occurrence

C3O has been detected by its microwave spectrum in the dark cold Taurus Molecular Cloud One [4] and also in the protostar Elias 18. [5]

The route to produce this is speculated to be: [6]

HC+
3 + CO2 → HC3O+ + CO
HC3O+ → C3O + H+

or [5]

C2 + CO → C3O which is more favourable at lower temperatures.

The related C3S is more abundant in dark molecular clouds, even though oxygen is 20 times more common than sulfur. The difference is due to the higher rate of formation and that C3S is less polar. [5]

Production

C3O can be produced by heating Meldrum's acid. This also produces acetone, carbon monoxide and carbon dioxide. [7]

R. L. DeKock and W. Waltner were the first to identify C3O by reacting atomic carbon with carbon monoxide in an argon matrix. They observed an infrared absorption line at 2241 cm−1. [7] They produced carbon atoms by heating graphite inside a thin tantalum tube. [8]

M. E. Jacox photolysed C3O2 in an argon matrix to produce C3O with an IR absorption line at 2244 cm−1, however he did not recognise what was produced. [8]

By heating diazocyclopentanetrione or a similar acid anhydride, (2,4-azo-3-oxo-dipentanoic anhydride), C3O is produced. Also the action of light on tetracarbon dioxide yields C3O and CO. [9]

Heating fumaryl chloride also yields C3O. [3] Heating Lead 2,4-dinitroresorcinate also produces C3O along with C2O, CO and carbon suboxide. [10] An electric discharge in carbon suboxide produces about 11 ppm C3O. [11]

Roger Brown heated 3,5-dimethyl-1-propynolpyrazole to over 700 °C to make C3O. [12] Also pyrolysis of 5,5'-bis(2,2-dimethyl-4,6-dioxo-1,3-dioxanylidene or di-isopropylidene ethylenetetracarboxylate yields C3O. [12]

Irradiating carbon monoxide ice with electrons yields a mixture of carbon oxides, including C3O. This process could happen on icy bodies in space. [13]

Reactions

C3O can be stabilised as a ligand in the pentacarbonyls of group 6 elements as in Cr(CO)5CCCO. This is formed from [n-Bu4N][CrI(CO)5] and the silver acetylide derivative of sodium propiolate (AgC≡CCOONa), and then thiophosgene. AgC≡CCOONa in turn is made from silver ions and sodium propiolate. [14] The blue black solid complex is called pentacarbony1(3-oxopropadienylidene)chromium(0). It is quite volatile and decomposes at 32 °C. Its infrared spectrum shows a band at 2028 cm−1 due to CCCO. The complex can dissolve in hexane, however it slowly decomposes, losing dicarbon (C2) which goes on to form acetylenes and cumulenes in the solvent. Dimethyl sulfoxide oxidises the CCCO ligand to carbon suboxide./ [15]

C3O deposits a reddish-black film on glass. [12]

The reaction of C3O and urea is predicted to form uracil. [16] The pathway for this, is that firstly the two molecules react to form isocyanuric acid and propiolamide, the NH then reacts to bond with the triple bond, with the NH2 group moving back. Then a final cyclisation occurs to make uracil. [17]

Properties

The C3O molecules do not last long. At the low pressure of 1 pascal, they survive about one second. [18] The force constants for the bonds are: C1-O 14.94, C1-C2 1.39 C2-C3 6.02 mdyn/Å. [8] The bond lengths are C-O 1.149, C1-C2 1.300, C2-C3 1.273 Å. The molecule is linear. [6]

bondatom 1atom 2length
Å [6] 		force constant
mdyn/Å [8] 		IR bands
cm−1
CCC-OC1O1.14914.94
CC-COC2C11.3001.39
C-CCCOC3C21.2736.02

Proton affinity is 885 kJmol−1. [6] The dipole moment is 2.391 D. [14] The oxygen end has a positive charge, and the carbon end the negative charge. [6] The molecule behaves as if there are triple bonds at each end, and a single bond in the middle. This is isoelectronic to cyanogen. [19]

Molecular constants used in determining the microwave spectrum are rotational constant B0=4810.8862 MHz centrifugal distortion constant D0=0.00077 MHz. Known microwave spectral lines vary from 9621.76 for J=1←0 to 182792.35 MHz for J=19←18. [11]

Related Research Articles

<span class="mw-page-title-main">Carbon monoxide</span> Colourless, odourless, tasteless and toxic gas

Carbon monoxide is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simplest carbon oxide. In coordination complexes, the carbon monoxide ligand is called carbonyl. It is a key ingredient in many processes in industrial chemistry.

<span class="mw-page-title-main">Oxide</span> Chemical compound where oxygen atoms are combined with atoms of other elements

An oxide is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– ion with oxygen in the oxidation state of −2. Most of the Earth's crust consists of oxides. Even materials considered pure elements often develop an oxide coating. For example, aluminium foil develops a thin skin of Al2O3 that protects the foil from further oxidation.

<span class="mw-page-title-main">Sulfur monoxide</span> Chemical compound

Sulfur monoxide is an inorganic compound with formula SO. It is only found as a dilute gas phase. When concentrated or condensed, it converts to S2O2 (disulfur dioxide). It has been detected in space but is rarely encountered intact otherwise.

<span class="mw-page-title-main">Carbon suboxide</span> Organic compound with structure O=C=C=C=O

Carbon suboxide, or tricarbon dioxide, is an organic, oxygen-containing chemical compound with formula C3O2 and structure O=C=C=C=O. Its four cumulative double bonds make it a cumulene. It is one of the stable members of the series of linear oxocarbons O=Cn=O, which also includes carbon dioxide and pentacarbon dioxide. Although if carefully purified it can exist at room temperature in the dark without decomposing, it will polymerize under certain conditions.

<span class="mw-page-title-main">Tricarbon</span> Chemical compound

Tricarbon is an inorganic compound with the chemical formula C
2(μ-C). It is a colourless gas that only persists in dilution or solution as an adduct. It is one of the simplest unsaturated carbenes. Tricarbon can be found in interstellar space and can be produced in the laboratory by a process called laser ablation.

<span class="mw-page-title-main">Dicarbon monoxide</span> Chemical compound

Dicarbon monoxide (C2O) is a molecule that contains two carbon atoms and one oxygen atom. It is a linear molecule that, because of its simplicity, is of interest in a variety of areas. It is, however, so extremely reactive that it is not encountered in everyday life. It is classified as a carbene, cumulene and an oxocarbon.

<span class="mw-page-title-main">Ethynyl radical</span> Hydrocarbon compound (•CCH)

The ethynyl radical (systematically named λ3-ethyne and hydridodicarbon(C—C)) is an organic compound with the chemical formula C≡CH (also written [CCH] or C
2H). It is a simple molecule that does not occur naturally on Earth but is abundant in the interstellar medium. It was first observed by electron spin resonance isolated in a solid argon matrix at liquid helium temperatures in 1963 by Cochran and coworkers at the Johns Hopkins Applied Physics Laboratory. It was first observed in the gas phase by Tucker and coworkers in November 1973 toward the Orion Nebula, using the NRAO 11-meter radio telescope. It has since been detected in a large variety of interstellar environments, including dense molecular clouds, bok globules, star forming regions, the shells around carbon-rich evolved stars, and even in other galaxies.

<span class="mw-page-title-main">Diatomic carbon</span> Chemical compound

Diatomic carbon (systematically named dicarbon and 1λ2,2λ2-ethene), is a green, gaseous inorganic chemical with the chemical formula C=C (also written [C2] or C2). It is kinetically unstable at ambient temperature and pressure, being removed through autopolymerisation. It occurs in carbon vapor, for example in electric arcs; in comets, stellar atmospheres, and the interstellar medium; and in blue hydrocarbon flames. Diatomic carbon is the second simplest of the allotropes of carbon (after atomic carbon), and is an intermediate participator in the genesis of fullerenes.

Formyl fluoride is the organic compound with the formula HC(O)F.

<span class="mw-page-title-main">Atomic carbon</span> Chemical compound

Atomic carbon, systematically named carbon and λ0-methane, is a colourless gaseous inorganic chemical with the chemical formula C. It is kinetically unstable at ambient temperature and pressure, being removed through autopolymerisation.

<span class="mw-page-title-main">Silicon monoxide</span> Chemical compound

Silicon monoxide is the chemical compound with the formula SiO where silicon is present in the oxidation state +2. In the vapour phase, it is a diatomic molecule. It has been detected in stellar objects and has been described as the most common oxide of silicon in the universe.

<span class="mw-page-title-main">Oxocarbon</span> Chemical compounds made of only carbon and oxygen

In chemistry, an oxocarbon or oxide of carbon is a chemical compound consisting only of carbon and oxygen. The simplest and most common oxocarbons are carbon monoxide (CO) and carbon dioxide. Many other stable or metastable oxides of carbon are known, but they are rarely encountered, such as carbon suboxide and mellitic anhydride.

<span class="mw-page-title-main">Formic anhydride</span> Chemical compound

Formic anhydride, also called methanoic anhydride, is an organic compound with the chemical formula C
2H
2O
3 and a structural formula of (H(C=O)−)2O. It can be viewed as the anhydride of formic acid (HCOOH).

<span class="mw-page-title-main">Disulfur monoxide</span> Chemical compound

Disulfur monoxide or sulfur suboxide is an inorganic compound with the formula S2O, one of the lower sulfur oxides. It is a colourless gas and condenses to give a roughly dark red coloured solid that is unstable at room temperature.

<span class="mw-page-title-main">Disulfur dioxide</span> Chemical compound

Disulfur dioxide, dimeric sulfur monoxide or SO dimer is an oxide of sulfur with the formula S2O2. The solid is unstable with a lifetime of a few seconds at room temperature.

Polycarbonyl, is a solid, metastable, and explosive polymer of carbon monoxide. The polymer is produced by exposing carbon monoxide to high pressures. The structure of the solid appears amorphous, but may include a zig zag of equally-spaced CO groups.

A heterocumulene is a molecule or ion containing a chain of at least three double bonds between consecutive atoms, in which one or more atoms in the doubly bonded chain is a heteroatom. Such species are analogous to a cumulene in which the chain of doubly bonded atoms contains only carbon, except that at least one carbon is replaced by a heteroatom. Some authors relax the definition to include species with chains of only two double bonds between consecutive atoms, also known as heteroallenes.

<span class="mw-page-title-main">Sulfoxylic acid</span> Chemical compound

Sulfoxylic acid (H2SO2) (also known as hyposulfurous acid or sulfur dihydroxide) is an unstable oxoacid of sulfur in an intermediate oxidation state between hydrogen sulfide and dithionous acid. It consists of two hydroxy groups attached to a sulfur atom. Sulfoxylic acid contains sulfur in an oxidation state of +2. Sulfur monoxide (SO) can be considered as a theoretical anhydride for sulfoxylic acid, but it is not actually known to react with water.

Tricarbon monosulfide (C3S) or tricarbon sulfur is a reactive molecular substance that has been detected in outer space. Tricarbon monosulfide is a heterocumulene or thiocumulene, consisting of a straight chain of three carbon atoms and a terminal sulfur atom.

<span class="mw-page-title-main">1,1-Dimethyldiborane</span> Chemical compound

1,1-Dimethyldiborane is the organoboron compound with the formula (CH3)2B(μ-H)2BH2. A pair of related 1,2-dimethyldiboranes are also known. It is a colorless gas that ignites in air.

References

  1. ↑ Brown, Ronald D.; Rice, E. H. (October 1984). "Tricarbon monoxide – a theoretical study". Journal of the American Chemical Society. 106 (22): 6475–6478. doi:10.1021/ja00334a002.
  2. ↑ Cooksy, A. L.; Watson, J. K. G.; Gottlieb, C. A.; Thaddeus, P. (February 1992). "The rotational spectrum of the carbon chain radical HCCCO". The Astrophysical Journal. 386: L27. Bibcode:1992ApJ...386L..27C. doi: 10.1086/186284 .
  3. 1 2 Ruppel, Raimund (1999). "Neue Heterokumulene und Carbene" (PDF) (in German). Gießen: Justus-Liebig-Universität: 13. Retrieved 10 November 2016.{{cite journal}}: Cite journal requires |journal= (help)
  4. ↑ Matthews, H. E.; Irvine, W. M.; Friberg, P; Brown, R. D.; Godfrey, P. D. (12 July 1984). "A new interstellar molecule: tricarbon monoxide". Nature. 310 (5973): 125–126. Bibcode:1984Natur.310..125M. doi:10.1038/310125a0. PMID   11541993. S2CID   4335136.
  5. 1 2 3 Abbas, Haider (6 February 2014). "Neutral-neutral reactions for the formation of C3O and C3S". Astrophysics and Space Science. 351 (1): 53–57. Bibcode:2014Ap&SS.351...53A. doi:10.1007/s10509-014-1809-y. S2CID   124813337.
  6. 1 2 3 4 5 Botschwina, Peter (1989). "A theoretical investigation of the astrophysically important molecules C3O and HC3O+". The Journal of Chemical Physics. 90 (8): 4301–4313. Bibcode:1989JChPh..90.4301B. doi:10.1063/1.455787.
  7. 1 2 Brown, Ronald D.; Eastwood, Frank W.; Elmes, Patricia S.; Godfrey, Peter D. (October 1983). "Tricarbon monoxide". Journal of the American Chemical Society. 105 (21): 6496–6497. doi:10.1021/ja00359a026. image of the tricarbon monoxide research team
  8. 1 2 3 4 DeKock, R. L.; Weltner, W. (December 1971). "C2O, CN2, and C3O molecules". Journal of the American Chemical Society. 93 (25): 7106–7107. doi:10.1021/ja00754a081.
  9. ↑ Maier, Günther; Reisenauer, Hans Peter; Balli, Heinz; Brandt, Willy; Janoschek, Rudolf (August 1990). "C4O2(1,2,3-Butatriene-1,4-dione), the First Dioxide of Carbon with an Even Number of C Atoms". Angewandte Chemie International Edition in English. 29 (8): 905–908. doi:10.1002/anie.199009051.
  10. ↑ Tang T.B. (1 February 1985). "Tricarbon monoxide and dicarbon monoxide: Addendum to "decomposition of lead (ii) 2,4-dinitroresorcinate"". Thermochimica Acta. 83 (2): 397–398. doi:10.1016/0040-6031(85)87024-6.
  11. 1 2 Tang, Tong B.; Inokuchi, Hiroo; Saito, Shuji; Yamada, Chikashi; Hirota, Eizi (April 1985). "CCCO: Generation by dc glow discharge in carbon suboxide, and microwave spectrum". Chemical Physics Letters. 116 (1): 83–85. Bibcode:1985CPL...116...83T. doi:10.1016/0009-2614(85)80130-5.
  12. 1 2 3 Brown, Roger F.C.; Godfrey, Peter D.; Lee, Swee Choo (1985). "Flash vacuum pyrolysis of 1-propynoylpyrazoles: a new precursor of tricarbon monoxide". Tetrahedron Letters. 26 (51): 6373–6376. doi:10.1016/S0040-4039(01)84602-5.
  13. ↑ Jamieson, Corey S.; Mebel, Alexander M.; Kaiser, Ralf I. (March 2006). "Understanding the Kinetics and Dynamics of Radiation‐induced Reaction Pathways in Carbon Monoxide Ice at 10 K". The Astrophysical Journal Supplement Series. 163 (1): 184–206. Bibcode:2006ApJS..163..184J. CiteSeerX   10.1.1.515.8473 . doi:10.1086/499245.
  14. 1 2 Baceiredo, Antoine (2010). Transition Metal Complexes of Neutral Eta1-Carbon Ligands. Springer Science & Business Media. pp. 247–248. ISBN   978-3642047213.
  15. ↑ Berke, Heinz; Härter, Peter (March 1980). "Complex Stabilization of 3-Oxopropadienylidene(C3O) with Pentacarbonylchromium(0)". Angewandte Chemie International Edition in English. 19 (3): 225–226. doi:10.1002/anie.198002251.
  16. ↑ Wang, Tianfang; Bowie, John H. (November 2011). "Studies of cyclization reactions of linear cumulenes and heterocumulenes using the neutralization-reionization procedure and/or ab initio calculations". Mass Spectrometry Reviews. 30 (6): 1225–1241. Bibcode:2011MSRv...30.1225W. doi:10.1002/mas.20328. PMID   21400561.
  17. ↑ Wang, Tianfang; Bowie, John H. (2012). "Can cytosine, thymine and uracil be formed in interstellar regions? A theoretical study". Org. Biomol. Chem. 10 (3): 652–662. doi:10.1039/C1OB06352A. PMID   22120518.
  18. ↑ Information, Reed Business (9 May 1985). "Theory predicts a new oxide of carbon". New Scientist (1455): 21. Retrieved 10 November 2016.{{cite journal}}: |first1= has generic name (help)
  19. ↑ Brown, Ronald D.; Pullin, David E.; Rice, Edward H. N.; Rodler, Martin (December 1985). "The infrared spectrum and force field of tricarbon monoxide". Journal of the American Chemical Society. 107 (26): 7877–7880. doi:10.1021/ja00312a013.
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