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.
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| Names | |||
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| IUPAC name
Sulfur monoxide[citation needed]
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| Systematic IUPAC name
Oxidosulfur[1] | |||
| Identifiers | |||
3D model (JSmol)
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| 7577656 | |||
| ChEBI | |||
| ChEMBL | |||
| ChemSpider | |||
| 666 | |||
| MeSH | sulfur+monoxide | ||
PubChem CID
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CompTox Dashboard (EPA)
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| Properties | |||
| SO | |||
| Molar mass | 48.064 g mol−1 | ||
| Appearance | Colourless gas | ||
| Reacts | |||
| log P | 0.155 | ||
| Thermochemistry | |||
Std molar
entropy (S⦵298) |
221.94 J K−1 mol−1 | ||
Std enthalpy of
formation (ΔfH⦵298) |
5.01 kJ mol−1 | ||
| Related compounds | |||
Related compounds
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Triplet oxygen Disulfur | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Structure and bonding
editThe 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
editThe 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
editIn 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
editLigand for transition metals
editAs a ligand SO can bond in a number different ways:[11][12]
- a terminal ligand, with a bent M−O−S arrangement, for example with titanium oxyfluoride[13]
- a terminal ligand, with a bent M−S−O arrangement, analogous to bent nitrosyl
- bridging across two or three metal centres (via sulfur), as in Fe3(μ3-S)(μ3-SO)(CO)9
- η2 sideways-on (d–π interaction) with vanadium, niobium, and tantalum.[14]
Astrochemistry
editSulfur 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
editSulfur 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
editBecause 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
editSulfur 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
edit
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]
References
edit- ^ "sulfur monoxide (CHEBI:45822)". Chemical Entities of Biological Interest. UK: European Bioinformatics Institute.
- ^ a b c d Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
- ^ 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.
- ^ 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.
- ^ Harpp, David N. (1997). "The sulfur diatomics". Phosphorus, Sulfur, and Silicon. 120. Amsterdam, NL: Gordon & Breach: 53. doi:10.1080/10426509708545509.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ 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) - ^ Woollins, J. D. (1995). "Sulfur: Inorganic Chemistry". Encyclopedia of Inorganic Chemistry. John Wiley and Sons. ISBN 0-471-93620-0.
- ^ 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.
- ^ 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.
- ^ Lellouch, E. (1996). "Io's atmosphere: Not yet understood". Icarus. 124: 1–21. doi:10.1006/icar.1996.0186.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ "Астрономический вестник. T. 54, Номер 2, 2020".
- ^ 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.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ a b 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.