Sulfur monoxide

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Sulfur monoxide
Skeletal formula of sulfur monoxide Sulfur monoxide.svg
Skeletal formula of sulfur monoxide
Spacefill model of sulfur monoxide Sulfur-monoxide-3D-vdW.png
Spacefill model of sulfur monoxide
Sulfur-monoxide-3D-balls.png
Names
IUPAC name
Sulfur monoxide[ citation needed ]
Systematic IUPAC name
Oxidosulfur [1]
Identifiers
3D model (JSmol)
7577656
ChEBI
ChEMBL
ChemSpider
666
MeSH sulfur+monoxide
PubChem CID
  • InChI=1S/OS/c1-2 Yes check.svgY
    Key: XTQHKBHJIVJGKJ-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/OS/c1-2
    Key: XTQHKBHJIVJGKJ-UHFFFAOYAK
  • O=S
Properties
SO
Molar mass 48.064 g mol−1
AppearanceColourless gas
Reacts
log P 0.155
Thermochemistry
Std molar
entropy (S⦵298)
221.94 J K−1 mol−1
5.01 kJ mol−1
Related compounds
Related compounds
 Triplet oxygen
Disulfur
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Sulfur monoxide is an inorganic compound with formula S O . 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.

Contents

Structure and bonding

The SO molecule has a triplet ground state similar to O2 and S2, that is, each molecule has two unpaired electrons. [2] The S−O bond length of 148.1 pm is similar to that found in lower sulfur oxides (e.g. S8O, S−O = 148 pm) but is longer than the S−O bond in gaseous S2O (146 pm), SO2 (143.1 pm) and SO3 (142 pm). [2]

The molecule is excited with near infrared radiation to the singlet state (with no unpaired electrons). The singlet state is believed to be more reactive than the ground triplet state, in the same way that singlet oxygen is more reactive than triplet oxygen. [3]

Production and reactions

The SO molecule is thermodynamically unstable, converting initially to S2O2. [2] Consequently controlled syntheses typically do not detect the presence of SO proper, but instead the reaction of a chemical trap or the terminal decomposition products of S2O2 (sulfur and sulfur dioxide).

Production of SO as a reagent in organic syntheses has centred on using compounds that "extrude" SO. Examples include the decomposition of the relatively simple molecule ethylene episulfoxide: [4]

C2H4SO → C2H4 + SO

Yields directly from an episulfoxide are poor, and improve only moderately when the carbons are sterically shielded. [5] A much better approach decomposes a diaryl cyclic trisulfide oxide, C10H6S3O, produced from thionyl chloride and the dithiol. [6]

SO inserts into alkenes, alkynes and dienes producing thiiranes, molecules with three-membered rings containing sulfur. [7]

Sulfur monoxide may form transiently during the metallic reduction of thionyl bromide. [8]

Generation under extreme conditions

In the laboratory, sulfur monoxide can be produced by treating sulfur dioxide with sulfur vapor in a glow discharge. [2] It has been detected in single-bubble sonoluminescence of concentrated sulfuric acid containing some dissolved noble gas. [9]

Benner and Stedman developed a chemiluminescence detector for sulfur via the reaction between sulfur monoxide and ozone: [10]

SO + O3 → SO2* + O2
SO2* → SO2 + hν

(* indicates an excited state)

Occurrence

Ligand for transition metals

As a ligand SO can bond in a number different ways: [11] [12]

Astrochemistry

Sulfur monoxide has been detected around Io, one of Jupiter's moons, both in the atmosphere [15] and in the plasma torus. [16] It has also been found in the atmosphere of Venus, [17] in Comet Hale–Bopp, [18] in 67P/Churyumov–Gerasimenko, [19] and in the interstellar medium. [20]

On Io, SO is thought to be produced both by volcanic and photochemical routes. The principal photochemical reactions are proposed as follows: [21]

O + S2 → S + SO
SO2 → SO + O

Sulfur monoxide has been found in NML Cygni. [22]

Biological chemistry

Sulfur monoxide may have some biological activity. The formation of transient SO in the coronary artery of pigs has been inferred from the reaction products, carbonyl sulfide and sulfur dioxide. [23]

Safety measures

Because of sulfur monoxide's rare occurrence in our atmosphere and poor stability, it is difficult to fully determine its hazards. But when condensed and compacted, it forms disulfur dioxide, which is relatively toxic and corrosive. This compound is also highly flammable (similar flammability to methane) and when burned produces sulfur dioxide, a poisonous gas.

Sulfur monoxide dication

Sulfur dioxide SO2 in presence of hexamethylbenzene C6(CH3)6 can be protonated under superacidic conditions (HF·AsF5) to give the non-rigid π-complex C6(CH3)6SO2+. The SO2+ moiety can essentially move barrierless over the benzene ring. The S−O bond length is 142.4(2) pm. [24]

C6(CH3)6 + SO2 + 3 HF·AsF5 → [C6(CH3)6SO][AsF6]2 + [H3O][AsF6]

Disulfur dioxide

The structure of disulfur dioxide, S2O2 Disulfur-dioxide-2D-dimensions.png
The structure of disulfur dioxide, S2O2
A space-filling model of the disulfur dioxide molecule Disulfur-dioxide-3D-vdW-A.png
A space-filling model of the disulfur dioxide molecule

SO converts to disulfur dioxide (S2O2). [25] Disulfur dioxide is a planar molecule with C2v symmetry. The S−O bond length is 145.8 pm, shorter than in the monomer, and the S−S bond length is 202.45 pm. The O−S−S angle is 112.7°. S2O2 has a dipole moment of 3.17  D. [25]

Related Research Articles

<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.

Sulfide (also sulphide in British English ) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. Sulfide also refers to large families of inorganic and organic compounds, e.g. lead sulfide and dimethyl sulfide. Hydrogen sulfide (H2S) and bisulfide (SH−) are the conjugate acids of sulfide.

In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation state. The reverse of disproportionation, such as when a compound in an intermediate oxidation state is formed from precursors of lower and higher oxidation states, is called comproportionation, also known as symproportionation.

Sulfur oxide refers to many types of sulfur and oxygen containing compounds such as SO, SO2, SO3, S7O2, S6O2, S2O2, etc.

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

Tetrasulfur tetranitride is an inorganic compound with the formula S4N4. This vivid orange, opaque, crystalline explosive is the most important binary sulfur nitride, which are compounds that contain only the elements sulfur and nitrogen. It is a precursor to many S-N compounds and has attracted wide interest for its unusual structure and bonding.

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

Disulfur decafluoride is a chemical compound with the formula S2F10. It was discovered in 1934 by Denbigh and Whytlaw-Gray. Each sulfur atom of the S2F10 molecule is octahedral, and surrounded by five fluorine atoms and one sulfur atom. The two sulfur atoms are connected by a single bond. In the S2F10 molecule, the oxidation state of each sulfur atoms is +5, but their valency is 6. S2F10 is highly toxic, with toxicity four times that of phosgene.

<span class="mw-page-title-main">Thiosulfate</span> Polyatomic ion (S2O3, charge –2)

Thiosulfate is an oxyanion of sulfur with the chemical formula S2O2−3. Thiosulfate also refers to the compounds containing this anion, which are the salts of thiosulfuric acid, such as sodium thiosulfate Na2S2O3 and ammonium thiosulfate (NH4)2S2O3. Thiosulfate salts occur naturally. Thiosulfate rapidly dechlorinates water, and is used to halt bleaching in the paper-making industry. Thiosulfate salts are mainly used for dyeing in textiles, and bleaching of natural substances.

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

Sulfur tetrafluoride is a chemical compound with the formula SF4. It is a colorless corrosive gas that releases dangerous hydrogen fluoride gas upon exposure to water or moisture. Sulfur tetrafluoride is a useful reagent for the preparation of organofluorine compounds, some of which are important in the pharmaceutical and specialty chemical industries.

<span class="mw-page-title-main">Lower sulfur oxides</span>

The lower sulfur oxides are a group of inorganic compounds with the formula SmOn, where 2m > n. These species are often unstable and thus rarely encountered in everyday life. They are significant intermediates in the combustion of elemental sulfur. Some well characterized examples include sulfur monoxide (SO), its dimer S2O2, and a series of cyclic sulfur oxides, SnOx (x = 1, 2), based on cyclic Sn rings.

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

Disulfur dinitride is the chemical compound with the formula S2N2.

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

Disulfur is the diatomic molecule with the formula S2. It is analogous to the dioxygen molecule but rarely occurs at room temperature. This violet gas is the dominant species in hot sulfur vapors. S2 is one of the minor components of the atmosphere of Io, which is predominantly composed of SO2. The instability of S2 is usually described in the context of the double bond rule.

Sulfur mononitride is an inorganic compound with the molecular formula SN. It is the sulfur analogue of and isoelectronic to the radical nitric oxide, NO. It was initially detected in 1975, in outer space in giant molecular clouds and later the coma of comets. This spurred further laboratory studies of the compound. Synthetically, it is produced by electric discharge in mixtures of nitrogen and sulfur compounds, or combustion in the gas phase and by photolysis in solution.

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

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.

In organometallic chemistry, metal sulfur dioxide complexes are complexes that contain sulfur dioxide, SO2, bonded to a transition metal. Such compounds are common but are mainly of theoretical interest. Historically, the study of these compounds has provided insights into the mechanisms of migratory insertion reactions.

<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.

In chemistry, molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula AOmXn, where X is a halogen. Known oxohalides have fluorine (F), chlorine (Cl), bromine (Br), and/or iodine (I) in their molecules. The element A may be a main group element, a transition element, a rare earth element or an actinide. The term oxohalide, or oxyhalide, may also refer to minerals and other crystalline substances with the same overall chemical formula, but having an ionic structure.

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

Thiophosphoryl fluoride is an inorganic molecular gas with formula PSF3 containing phosphorus, sulfur and fluorine. It spontaneously ignites in air and burns with a cool flame. The discoverers were able to have flames around their hands without discomfort, and called it "probably one of the coldest flames known". The gas was discovered in 1888.

The chalcogens react with each other to form interchalcogen compounds.

<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.

Dihydroxydisulfane or hypodithionous acid is a reduced sulfur oxyacid with sulfur in a formal oxidation state of +1, but the valence of sulfur is 2. The structural formula is HO−S−S−OH, with all atoms arranged in a chain. It is an isomer of thiosulfurous acid but is lower in energy. Other isomers include HOS(=O)SH, HOS(=S)OH, and HS(=O)2SH. Disulfur monoxide, S2O, can be considered as the anhydride. Unlike many of these other reduced sulfur acids, dihydroxydisulfane can be formed in a pure state by reacting hydrogen sulfide with sulfur dioxide at −70 °C in dichlorodifluoromethane.

References

  1. ↑ "sulfur monoxide (CHEBI:45822)". Chemical Entities of Biological Interest. UK: European Bioinformatics Institute.
  2. 1 2 3 4 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  3. ↑ Salama, F.; Frei, H. J. (1989). "Near-Infrared-Light-Induced Reaction of Singlet SO with Allene and Dimethylacetylene in a Rare Gas Matrix. Infrared Spectra of Two Novel Episulfoxides". Journal of Physical Chemistry. 93: 1285–1292. doi:10.1021/j100341a023.
  4. ↑ Chao, P.; Lemal, D. M. (1973). "Sulfur Monoxide Chemistry. The Nature of SO from Thiirane Oxide and the Mechanism of Its Reaction with Dienes". Journal of the American Chemical Society. 95 (3): 920. doi:10.1021/ja00784a049.
  5. ↑ Harpp, David N. (1997). "The sulfur diatomics". Phosphorus, Sulfur, and Silicon. 120. Amsterdam, NL: Gordon & Breach: 53. doi:10.1080/10426509708545509.
  6. ↑ Grainger, R. S.; Procopio, A.; Steed, J. W. (2001). "A Novel Recyclable Sulfur Monoxide Transfer Reagent". Organic Letters. 3 (22): 3565–3568. doi:10.1021/ol016678g. PMID   11678709.
  7. ↑ Nakayama, J.; Tajima, Y.; Piao, X.-H.; Sugihara, Y. (2007). "[1+2] Cycloadditions of Sulfur Monoxide (SO) to Alkenes and Alkynes and [1+4]Cycloadditions to Dienes (Polyenes). Generation and Reactions of Singlet SO?". Journal of the American Chemical Society. 129 (23): 7250–7251. doi:10.1021/ja072044e. PMID   17506566.
  8. ↑ Magee, Philip S. (1971). "The Sulfur–Bromine Bond". In Senning, Alexander (ed.). Sulfur in Organic and Inorganic Chemistry. Vol. 1. New York: Marcel Dekker. pp. 271–276. ISBN   0-8247-1615-9. LCCN   70-154612.
  9. ↑ Suslick, K. S.; Flannigan, D. J. (2004). "The temperatures of single-bubble sonoluminescence (A)". The Journal of the Acoustical Society of America. 116 (4): 2540. Bibcode:2004ASAJ..116.2540S. doi:10.1121/1.4785135.
  10. ↑ Benner, R. L.; Stedman, D. H. (1994). "Chemical Mechanism and Efficiency of the Sulfur Chemiluminescence Detector". Applied Spectroscopy. 48 (7): 848–851. Bibcode:1994ApSpe..48..848B. doi:10.1366/0003702944029901. S2CID   98849015.
  11. ↑ Schenk, W. A. (1987). "Sulfur Oxides as Ligands in Coordination Compounds. Angewandte Chemie International Edition in English". 26: 98–109. doi:10.1002/anie.198700981.{{cite journal}}: Cite journal requires |journal= (help)
  12. ↑ Woollins, J. D. (1995). "Sulfur: Inorganic Chemistry". Encyclopedia of Inorganic Chemistry. John Wiley and Sons. ISBN   0-471-93620-0.
  13. ↑ Wei, R.; Chen, X.; Gong, Y. (2019). "End-On Oxygen-Bound Sulfur Monoxide Complex of Titanium Oxyfluoride". Inorganic Chemistry. 58 (17): 11801–11806. doi:10.1021/acs.inorgchem.9b01880. PMID   31441297. S2CID   201617509.
  14. ↑ Wei, R.; Chen, X.; Gong, Y. (2019). "Side-On Sulfur Monoxide Complexes of Tantalum, Niobium, and Vanadium Oxyfluorides". Inorganic Chemistry. 58 (6): 3807–3814. doi:10.1021/acs.inorgchem.8b03411. PMID   30707575. S2CID   73438027.
  15. ↑ Lellouch, E. (1996). "Io's atmosphere: Not yet understood". Icarus. 124: 1–21. doi:10.1006/icar.1996.0186.
  16. ↑ Russell, C. T.; Kivelson, M. G. (2000). "Detection of SO in Io's Exosphere". Science. 287 (5460): 1998–1999. Bibcode:2000Sci...287.1998R. doi:10.1126/science.287.5460.1998. PMID   10720321.
  17. ↑ Na, C. Y.; Esposito, L. W.; Skinner, T. E. (1990). "International Ultraviolet Explorer observations of Venus SO2 and SO". Journal of Geophysical Research. 95: 7485–7491. Bibcode:1990JGR....95.7485N. doi:10.1029/JD095iD06p07485.
  18. ↑ Lis, D. C.; Mehringer, D. M.; Benford, D.; Gardner, M.; Phillips, T. G.; Bockelée-Morvan, D.; Biver, N.; Colom, P.; Crovisier, J.; Despois, D.; Rauer, H. (1997). "New Molecular Species in Comet C/1995 O1 (Hale–Bopp) Observed with the Caltech S submillimeter Observatory". Earth, Moon, and Planets. 78 (1–3): 13–20. Bibcode:1997EM&P...78...13L. doi:10.1023/A:1006281802554. S2CID   51862359.
  19. ↑ "Астрономический вестник. T. 54, Номер 2, 2020".
  20. ↑ Gottlieb, C. A.; Gottlieb, E. W.; Litvak, M. M.; Ball, J. A.; Pennfield, H. (1978). "Observations of interstellar sulfur monoxide". Astrophysical Journal. 1 (219): 77–94. Bibcode:1978ApJ...219...77G. doi:10.1086/155757.
  21. ↑ Moses, J. I.; Zolotov, M. Y.; Fegley, B. (2002). "Photochemistry of a Volcanically Driven Atmosphere on Io: Sulfur and Oxygen Species from a Pele-Type Eruption". Icarus. 156 (1): 76–106. Bibcode:2002Icar..156...76M. doi:10.1006/icar.2001.6758.
  22. ↑ Marvel, Kevin (1996). "NML Cygni". The Circumstellar Environment of Evolved Stars As Revealed by Studies of Circumstellar Water Masers. Universal Publishers. pp. 182–212. ISBN   978-1-58112-061-5 . Retrieved 23 August 2012.
  23. ↑ Balazy, M.; Abu-Yousef, I. A.; Harpp, D. N.; Park, J. (2003). "Identification of carbonyl sulfide and sulfur dioxide in porcine coronary artery by gas chromatography/mass spectrometry, possible relevance to EDHF". Biochemical and Biophysical Research Communications. 311 (3): 728–734. doi:10.1016/j.bbrc.2003.10.055. PMID   14623333.
  24. ↑ Malischewski, Moritz; Seppelt, Konrad (2017). "Isolation and Characterization of a Non-Rigid Hexamethylbenzene-SO2+ Complex" (PDF). Angewandte Chemie International Edition. 56 (52): 16495–16497. doi:10.1002/anie.201708552. ISSN   1433-7851. PMID   29084371. S2CID   27260554.
  25. 1 2 Lovas, F. J.; Tiemann, E.; Johnson, D. R. (1974). "Spectroscopic studies of the SO2 discharge system. II. Microwave spectrum of the SO dimer". The Journal of Chemical Physics. 60 (12): 5005–5010. Bibcode:1974JChPh..60.5005L. doi:10.1063/1.1681015.
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