Carbon suboxide

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Carbon suboxide
Carbon-suboxide-2D-dimensions.svg
Carbon-suboxide-3D-vdW.png
Names
Preferred IUPAC name
Propa-1,2-diene-1,3-dione
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
MeSH Carbon+suboxide
PubChem CID
UNII
  • InChI=1S/C3O2/c4-2-1-3-5 Yes check.svgY
    Key: GNEVIACKFGQMHB-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C3O2/c4-2-1-3-5
    Key: GNEVIACKFGQMHB-UHFFFAOYAU
  • O=C=C=C=O
Properties
C3O2
Molar mass 68.031 g·mol−1
Appearancecolorless gas
Odor strong, pungent odor
Density 3.0 kg/m3, gas [1]

1.114 g/cm3, liquid [2]

Melting point −111.3 °C (−168.3 °F; 161.8 K)
Boiling point 6.8 °C (44.2 °F; 279.9 K)
reacts
Solubility soluble in 1,4-dioxane, ether, xylene, CS2, tetrahydrofuran
1.4538 (6 °C)
0 D
Structure
rhombic
quasilinear (phase dependent)
Thermochemistry
66.99 J/mol K
Std molar
entropy (S⦵298)
276.1 J/mol K
−93.6 kJ/mol
Related compounds
Related oxides
 carbon dioxide
carbon monoxide
dicarbon monoxide
Related compounds
 carbon subsulfide
carbon subnitride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

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 (CO2) and pentacarbon dioxide (C5O2). Although if carefully purified it can exist at room temperature in the dark without decomposing, it will polymerize under certain conditions.

Contents

The substance was discovered in 1873 by Benjamin Brodie by subjecting carbon monoxide to an electric current. He claimed that the product was part of a series of "oxycarbons" with formulas Cx+1Ox, namely C2O, C3O2, C4O3, C5O4, …, and to have identified the last two; [3] [4] however, only C3O2 is known. In 1891 Marcellin Berthelot observed that heating pure carbon monoxide at about 550 °C created small amounts of carbon dioxide but no trace of carbon, and assumed that a carbon-rich oxide was created instead, which he named "sub-oxide". He assumed it was the same product obtained by electric discharge and proposed the formula C2O. [5] Otto Diels later stated that the more organic names dicarbonylmethane and dioxallene were also correct.

It is commonly described as an oily liquid or gas at room temperature with an extremely noxious odor. [6]

Synthesis

It is synthesized by warming a dry mixture of phosphorus pentoxide (P4O10) and malonic acid or its esters. [7] Therefore, it can be also considered as the anhydride of malonic anhydride, i.e. the "second anhydride" of malonic acid. [8]

Several other ways for synthesis and reactions of carbon suboxide can be found in a review from 1930 by Reyerson. [6]

Polymerization

Carbon suboxide polymerizes spontaneously to a red, yellow, or black solid. The structure is postulated to be poly(α-pyronic), similar to the structure in 2-pyrone (α-pyrone). [9] [10] The number of monomers in the polymers is variable (see Oxocarbon#Polymeric carbon oxides). In 1969, it was hypothesized that the color of the Martian surface was caused by this compound; this was disproved by the Viking Mars probes (the red color is instead due to iron oxide). [11]

Uses

Carbon suboxide is used in the preparation of malonates; and as an auxiliary to improve the dye affinity of furs.

In chemical synthesis, carbon suboxide is a 1,3-dipole, reacting with alkenes to make 1,3‑cyclopentadiones. Because it is so unstable, it is a reagent of last resort. [12]

Biological role

Those are 6- or 8-ring macrocyclic polymers of carbon suboxide that were found in living organisms. They are acting as an endogenous digoxin-like Na+/K+-ATP-ase and Ca-dependent ATP-ase inhibitors, endogenous natriuretics, antioxidants and antihypertensives Carbon suboxide macrocyclic polymers.gif
Those are 6- or 8-ring macrocyclic polymers of carbon suboxide that were found in living organisms. They are acting as an endogenous digoxin-like Na+/K+-ATP-ase and Ca-dependent ATP-ase inhibitors, endogenous natriuretics, antioxidants and antihypertensives

Carbon suboxide, C3O2, can be produced in small amounts in any biochemical process that normally produces carbon monoxide, CO, for example, during heme oxidation by heme oxygenase-1. It can also be formed from malonic acid. It has been shown that carbon suboxide in an organism can quickly polymerize into macrocyclic polycarbon structures with the common formula (C3O2)n (mostly (C3O2)6 and (C3O2)8), and that those macrocyclic compounds are potent inhibitors of Na+/K+-ATP-ase and Ca-dependent ATP-ase, and have digoxin-like physiological properties and natriuretic and antihypertensive actions. Those macrocyclic carbon suboxide polymer compounds are thought to be endogenous digoxin-like regulators of Na+/K+-ATP-ases and Ca-dependent ATP-ases, and endogenous natriuretics and antihypertensives. [13] [14] [15] Other than that, some authors think also that those macrocyclic compounds of carbon suboxide can possibly diminish free radical formation and oxidative stress and play a role in endogenous anticancer protective mechanisms, for example in the retina. [16]

Structure and bonding

The structure of carbon suboxide has been the subject of experiments and computations since the 1970s. The central issue is the question of whether the molecule is linear or bent (i.e., whether ). Studies generally agree that the molecule is highly non-rigid, with a very shallow barrier to bending. According to one study, the molecular geometry is described by a double-well potential with a minimum at θC2 ~ 160°, an inversion barrier of 20 cm−1 (0.057 kcal/mol), and a total energy change of 80 cm−1 (0.23 kcal/mol) for 140° ≤ θC2 ≤ 180°. [17] The small energetic barrier to bending is around the same order of magnitude as the vibrational zero-point energy. Therefore, the molecule is best described as quasilinear. While infrared [18] and electron diffraction [19] studies have indicated that C3O2 has a bent structure in the gas phase, the compound was found to possess at least an average linear geometry in the solid phase by X-ray crystallography, although the large thermal ellipsoids of the oxygen atoms and C2 have been interpreted to be consistent with rapid bending (minimum θC2 ~ 170°), even in the solid state. [10]

A heterocumulene resonance form of carbon suboxide based on minimization of formal charges does not readily explain the molecule's non-rigidity and deviation from linearity. To account for the quasilinear structure of carbon suboxide, Frenking has proposed that carbon suboxide be regarded as a "coordination complex" of carbon(0) bearing two carbonyl ligands and two lone pairs: . [20] However, the contribution of dative bonding in C3O2 and similar species has been criticized as chemically unreasonable by others. [21]

Carbon suboxide dative.png

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.

Carbon compounds are defined as chemical substances containing carbon. More compounds of carbon exist than any other chemical element except for hydrogen. Organic carbon compounds are far more numerous than inorganic carbon compounds. In general bonds of carbon with other elements are covalent bonds. Carbon is tetravalent but carbon free radicals and carbenes occur as short-lived intermediates. Ions of carbon are carbocations and carbanions are also short-lived. An important carbon property is catenation as the ability to form long carbon chains and rings.

<span class="mw-page-title-main">Organic compound</span> Chemical compound with carbon-hydrogen bonds

Some chemical authorities define an organic compound as a chemical compound that contains a carbon–hydrogen or carbon–carbon bond; others consider an organic compound to be any chemical compound that contains carbon. For example, carbon-containing compounds such as alkanes and its derivatives are universally considered organic, but many others are sometimes considered inorganic, such as halides of carbon without carbon-hydrogen and carbon-carbon bonds, and certain compounds of carbon with nitrogen and oxygen.

<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.

In organic chemistry, the Swern oxidation, named after Daniel Swern, is a chemical reaction whereby a primary or secondary alcohol is oxidized to an aldehyde or ketone using oxalyl chloride, dimethyl sulfoxide (DMSO) and an organic base, such as triethylamine. It is one of the many oxidation reactions commonly referred to as 'activated DMSO' oxidations. The reaction is known for its mild character and wide tolerance of functional groups.

<span class="mw-page-title-main">Epoxide</span> Organic compounds with a carbon-carbon-oxygen ring

In organic chemistry, an epoxide is a cyclic ether, where the ether forms a three-atom ring: two atoms of carbon and one atom of oxygen. This triangular structure has substantial ring strain, making epoxides highly reactive, more so than other ethers. They are produced on a large scale for many applications. In general, low molecular weight epoxides are colourless and nonpolar, and often volatile.

<span class="mw-page-title-main">Malonic acid</span> Carboxylic acid with chemical formula CH2(COOH)2

Malonic acid (IUPAC systematic name: propanedioic acid) is a dicarboxylic acid with structure CH2(COOH)2. The ionized form of malonic acid, as well as its esters and salts, are known as malonates. For example, diethyl malonate is malonic acid's diethyl ester. The name originates from the Greek word μᾶλον (malon) meaning 'apple'.

<span class="mw-page-title-main">Vanadium(V) oxide</span> Precursor to vanadium alloys and industrial catalyst

Vanadium(V) oxide (vanadia) is the inorganic compound with the formula V2O5. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because of its high oxidation state, it is both an amphoteric oxide and an oxidizing agent. From the industrial perspective, it is the most important compound of vanadium, being the principal precursor to alloys of vanadium and is a widely used industrial catalyst.

<span class="mw-page-title-main">Meldrum's acid</span> Chemical compound

Meldrum's acid or 2,2-dimethyl-1,3-dioxane-4,6-dione is an organic compound with formula C6H8O4. Its molecule has a heterocyclic core with four carbon and two oxygen atoms; the formula can also be written as [−O−(C 2)−O−(C=O)−(CH2)−(C=O)−].

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

Dicarbon monoxide 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">Iodine pentoxide</span> Chemical compound

Iodine pentoxide is the chemical compound with the formula I2O5. This iodine oxide is the anhydride of iodic acid, and the only stable oxide of iodine. It is produced by dehydrating iodic acid at 200 °C in a stream of dry air:

<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">Pentacarbon dioxide</span> Chemical compound

Pentacarbon dioxide, officially penta-1,2,3,4-tetraene-1,5-dione, is an oxide of carbon (an oxocarbon) with formula C5O2 or O=C=C=C=C=C=O.

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

Malonic anhydride or oxetane-2,4-dione is an organic compound with chemical formula C3H2O3 or CH2(CO)2O. It can be viewed as the anhydride of malonic acid, or a double ketone of oxetane.

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

Tetracarbon dioxide is an oxide of carbon, a chemical compound of carbon and oxygen, with chemical formula C4O2 or O=C=C=C=C=O. It can be regarded as butatriene dione, the double ketone of butatriene — more precisely 1,2,3-butatriene-1,4-dione.

An insertion reaction is a chemical reaction where one chemical entity interposes itself into an existing bond of typically a second chemical entity e.g.:

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.

Gaseous signaling molecules are gaseous molecules that are either synthesized internally (endogenously) in the organism, tissue or cell or are received by the organism, tissue or cell from outside and that are used to transmit chemical signals which induce certain physiological or biochemical changes in the organism, tissue or cell. The term is applied to, for example, oxygen, carbon dioxide, sulfur dioxide, nitrous oxide, hydrogen cyanide, ammonia, methane, hydrogen, ethylene, etc.

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

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.

<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.

References

  1. ↑ "Carbon Suboxide". WebElements Periodic Table. Retrieved 19 Feb 2019.
  2. ↑ Weast RC, Astle MJ, eds. (1983). CRC Handbook of Chemistry and Physics (64th ed.). Boca Raton: CRC Press. p. B-82. ISBN   9780849304637.
  3. ↑ Brodie BC (1873). "Note on the Synthesis of Marsh-Gas and Formic Acid, and on the Electric Decomposition of Carbonic Oxide". Proc. R. Soc. Lond. 21 (139–147): 245–247. doi: 10.1098/rspl.1872.0052 . JSTOR   113037. When pure and dry carbonic oxide [=carbon monoxide] is circulated through the induction-tube, and there submitted to the action of electricity, a decomposition of the gas occurs [...] Carbonic acid [=carbon dioxide] is formed, and simultaneously with its formation a solid deposit may be observed in the induction-tube. This deposit appears as a transparent film of a red-brown color, lining the walls of the tube. It is perfectly soluble in water, which is strongly colored by it. The solution has an intensely acid reaction. The solid deposit, in the dry condition before it has been in contact with the water, is an oxide of carbon.
  4. ↑ Brodie BC (1873). "Ueber eine Synthese von Sumpfgas und Ameisensäure und die electrische Zersetzung des Kohlenoxyds". Liebigs Ann. 169 (1–2): 270–271. doi:10.1002/jlac.18731690119.
  5. ↑ Berthelot M (1891). "Action de la chaleur sur l'oxyde de carbone". Annales de Chimie et de Physique . 6 (24): 126–132. Archived from the original on 17 February 2012. Retrieved 21 Feb 2007.
  6. 1 2 Reyerson LH, Kobe K (1930). "Carbon Suboxide". Chem. Rev. 7 (4): 479–492. doi:10.1021/cr60028a002.
  7. ↑ Diels O, Wolf B (1906). "Ueber das Kohlensuboxyd. I". Chem. Ber. 39: 689–697. doi:10.1002/cber.190603901103.
  8. ↑ Perks HM, Liebman JF (2000). "Paradigms and Paradoxes: Aspects of the Energetics of Carboxylic Acids and Their Anhydrides". Structural Chemistry. 11 (4): 265–269. doi:10.1023/A:1009270411806. S2CID   92816468.
  9. ↑ Ballauff M, Li L, Rosenfeldt S, et al. (2004). "Analysis of Poly(carbon suboxide) by Small-Angle X-ray Scattering". Angewandte Chemie International Edition . 43 (43): 5843–5846. doi:10.1002/anie.200460263. PMID   15523711.
  10. 1 2 Ellern A, Drews T, Seppelt K (2001). "The Structure of Carbon Suboxide, C3O2, in the Solid State". Z. Anorg. Allg. Chem. 627 (1): 73–76. doi:10.1002/1521-3749(200101)627:1<73::AID-ZAAC73>3.0.CO;2-A.
  11. ↑ Plummer WT, Carsont RK (1969). "Mars: Is the Surface Colored by Carbon Suboxide?". Science . 166 (3909): 1141–1142. Bibcode:1969Sci...166.1141P. doi:10.1126/science.166.3909.1141. PMID   17775571. S2CID   31568906.
  12. ↑ "Carbon suboxide". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rc015.
  13. ↑ Kerek F (2000). "The structure of the digitalislike and natriuretic factors identified as macrocyclic derivatives of the inorganic carbon suboxide". Hypertension Research. 23 (Suppl S33): S33–38. doi: 10.1291/hypres.23.Supplement_S33 . PMID   11016817.
  14. ↑ Stimac R, Kerek F, Apell HJ (2003). "Macrocyclic carbon suboxide oligomers as potent inhibitors of the Na,K-ATPase". Ann. N. Y. Acad. Sci. 986 (1): 327–329. Bibcode:2003NYASA.986..327S. doi:10.1111/j.1749-6632.2003.tb07204.x. PMID   12763840.
  15. ↑ Kerek F, Stimac R, Apell HJ, et al. (2002). "Characterization of the macrocyclic carbon suboxide factors as potent Na,K-ATPase and SR Ca-ATPase inhibitors". Biochimica et Biophysica Acta (BBA) - Biomembranes . 1567 (1–2): 213–220. doi: 10.1016/S0005-2736(02)00609-0 . PMID   12488055.
  16. ↑ Tubaro E (1966). "Carbon suboxide, the probable precursor of an antitumor cellular substance: retina". Bollettino Chimico Farmaceutico (in Italian). 105 (6): 415–416. PMID   6005012.
  17. ↑ Brown RD (1993). "Structural Information on Large Amplitude Motions". In Laane J, Dakkouri M, Veken Bv, et al. (eds.). Structures and Conformations of Non-Rigid Molecules. NATO ASI Series. Vol. 410. Springer Netherlands. pp. 99–112. doi:10.1007/978-94-011-2074-6_5. ISBN   9789401049207.
  18. ↑ Jensen P, Johns JW (1986). "The infrared spectrum of carbon suboxide in the ν6 fundamental region: Experimental observation and semirigid bender analysis". J. Mol. Spectrosc. 118 (1): 248–266. Bibcode:1986JMoSp.118..248J. doi:10.1016/0022-2852(86)90239-0.
  19. ↑ Clark A (1970). "The potential function for the CCC bending in carbon suboxide". Chem. Phys. Lett. 6 (5): 452–456. Bibcode:1970CPL.....6..452C. doi:10.1016/0009-2614(70)85190-9.
  20. ↑ Frenking G, Tonner R (2009). "Divalent carbon(0) compounds". Pure Appl. Chem. 81 (4): 597–614. doi: 10.1351/pac-con-08-11-03 . ISSN   1365-3075. S2CID   98257123.
  21. ↑ Himmel D, Krossing I, Schnepf A (2014). "Dative Bonds in Main-Group Compounds: A Case for Fewer Arrows!". Angewandte Chemie International Edition. 53 (2): 370–374. doi:10.1002/anie.201300461. ISSN   1521-3773. PMID   24243854.
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