Disulfur monoxide: Difference between revisions
reorganize slightly, esp lede. Cite Steudels review, consolidate prep and history, put structure in lede since it was a one-sentence section, revised history in slightly less dramatic wording |
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S<sub>2</sub>O can be found coming from volcanoes on [[Io (moon)|Io]]. It can form from 1 to 6% when hot 100 bar S<sub>2</sub> and SO<sub>2</sub> gas erupts from volcanoes. It is believed that [[Pele (volcano)|Pele]] on Io is surrounded by solid S<sub>2</sub>O.<ref>{{cite journal|url=http://zolotov.faculty.asu.edu/publ/Io-S2O-1998.pdf|author=Mikhail Yu. Zolotov and Bruce Fegley|title=Volcanic Origin of Disulfur Monoxide (S2O) on Io|journal=Icarus|volume=133|page=293|date=9 March 1998|doi=10.1006/icar.1998.5930|issue=2 |bibcode = 1998Icar..133..293Z }}</ref> |
S<sub>2</sub>O can be found coming from volcanoes on [[Io (moon)|Io]]. It can form from 1 to 6% when hot 100 bar S<sub>2</sub> and SO<sub>2</sub> gas erupts from volcanoes. It is believed that [[Pele (volcano)|Pele]] on Io is surrounded by solid S<sub>2</sub>O.<ref>{{cite journal|url=http://zolotov.faculty.asu.edu/publ/Io-S2O-1998.pdf|author=Mikhail Yu. Zolotov and Bruce Fegley|title=Volcanic Origin of Disulfur Monoxide (S2O) on Io|journal=Icarus|volume=133|page=293|date=9 March 1998|doi=10.1006/icar.1998.5930|issue=2 |bibcode = 1998Icar..133..293Z }}</ref> |
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==Properties== |
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Condensed solid S<sub>2</sub>O displays absorption bands at 420 and 530 nm. These are likely to be due to S<sub>3</sub> and S<sub>4</sub>.<ref name=Nav10>{{cite journal|last1=Navizet|first1=Isabelle|last2=Komiha|first2=Najia|last3=Linguerri|first3=Roberto|last4=Chambaud|first4=Gilberte|last5=Rosmus|first5=Pavel|title=On the formation of S2O at low energies: An ab initio study|journal=Chemical Physics Letters|date=November 2010|volume=500|issue=4-6|pages=207–210|doi=10.1016/j.cplett.2010.10.012}}</ref> |
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The microwave spectrum of S<sub>2</sub>O has the following rotational parameters: A=41915.44, B=5059.07, and C=4507.19 MHz.<ref>{{cite journal|last1=Cook|first1=Robert L|last2=Winnewisser|first2=Gisbert|last3=Lindsey|first3=D.C|title=The centrifugal distortion constants of disulfur monoxide|journal=Journal of Molecular Spectroscopy|date=May 1973|volume=46|issue=2|pages=276–284|doi=10.1016/0022-2852(73)90042-8}}</ref> |
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In the ultraviolet S<sub>2</sub>O has absorption bands at 3235 and 3278 Å.<ref name=Hall77>{{cite journal|last1=Hallin|first1=K-E. J.|last2=Merer|first2=A. J.|last3=Milton|first3=D. J.|title=Rotational analysis of bands of the 3400 Å system of disulphur monoxide (S2O)|journal=Canadian Journal of Physics|date=November 1977|volume=55|issue=21|pages=1858–1867|doi=10.1139/p77-226}}</ref> |
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The bond angle SSO is 109°.<ref name=Hall77/> |
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==Reactions== |
==Reactions== |
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A self decomposition of S<sub>2</sub>O can form [[trithio-ozone]] (S<sub>3</sub>) and SO<sub>2</sub>. Also ''5,6-di-tert-butyl-2,3,7-trithiabicyclo[2.2.1]hept-5-ene 2-endo-7-endo-dioxide'' when heated can form S<sub>2</sub>O.<ref>{{cite journal|title=Reversible disulfur monoxide (S2O)-forming retro-Diels-Alder reaction. disproportionation of S2O to trithio-ozone (S3) and sulfur dioxide (SO2) and reactivities of S2O and S3|first6=A|last6=Ishii|first5=Y|last5=Sugihara|first4=A|last4=Sakamoto|first3=J|last3=Takayama|first2=S|last2=Aoki|author=Nakayama J|journal=Journal of the American Chemical Societ|date=28 July 2004|volume=126|issue=29|pmid=15264842|doi=10.1021/ja047729i|pages=9085–93}}</ref> It reacts with diazoalkanes to form dithiirane 1-oxides.<ref>{{cite journal|title=A Convenient Method for the Generation of a Disulfur Monoxide Equivalent and Its Reaction with Diazoalkanes to Yield Dithiirane 1-Oxides|first5=J|last5=Nakayama|first4=H|last4=Oshida|first3=K|last3=Tekura|first2=T|last2=Kawai|author=A Ishii|journal=Angew Chem Int Ed Engl|date=18 May 2001|pages=1924–1926|volume=40|issue=10|pmid=11385674|doi=10.1002/1521-3773(20010518)40:10<1924::AID-ANIE1924>3.0.CO;2-F}}</ref> |
A self decomposition of S<sub>2</sub>O can form [[trithio-ozone]] (S<sub>3</sub>) and SO<sub>2</sub>. Also ''5,6-di-tert-butyl-2,3,7-trithiabicyclo[2.2.1]hept-5-ene 2-endo-7-endo-dioxide'' when heated can form S<sub>2</sub>O.<ref>{{cite journal|title=Reversible disulfur monoxide (S2O)-forming retro-Diels-Alder reaction. disproportionation of S2O to trithio-ozone (S3) and sulfur dioxide (SO2) and reactivities of S2O and S3|first6=A|last6=Ishii|first5=Y|last5=Sugihara|first4=A|last4=Sakamoto|first3=J|last3=Takayama|first2=S|last2=Aoki|author=Nakayama J|journal=Journal of the American Chemical Societ|date=28 July 2004|volume=126|issue=29|pmid=15264842|doi=10.1021/ja047729i|pages=9085–93}}</ref> It reacts with diazoalkanes to form dithiirane 1-oxides.<ref>{{cite journal|title=A Convenient Method for the Generation of a Disulfur Monoxide Equivalent and Its Reaction with Diazoalkanes to Yield Dithiirane 1-Oxides|first5=J|last5=Nakayama|first4=H|last4=Oshida|first3=K|last3=Tekura|first2=T|last2=Kawai|author=A Ishii|journal=Angew Chem Int Ed Engl|date=18 May 2001|pages=1924–1926|volume=40|issue=10|pmid=11385674|doi=10.1002/1521-3773(20010518)40:10<1924::AID-ANIE1924>3.0.CO;2-F}}</ref> |
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Revision as of 22:50, 10 June 2015
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| Names | |
|---|---|
| Other names
sulfur suboxide; Sulfuroxide;
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| Identifiers | |
| ChemSpider | |
CompTox Dashboard (EPA)
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| Properties | |
| S2O | |
| Molar mass | 80.1294 g/mol[1] |
| Appearance | colourless gas or dark red solid[2] |
| Structure | |
| bent | |
| Hazards | |
| Occupational safety and health (OHS/OSH): | |
Main hazards
|
toxic |
| Related compounds | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
| |
Disulfur monoxide or sulfur suboxide is an inorganic compound with formula S2O. It is one of the lower sulfur oxides. It is a colourless gas and condenses to give a pale coloured solid that is unstable at room temperature.[3] It is a bent molecule with an S-S-O angle of 117.88°, S-S bond length of 188.4pm, and S-O bond length of 146.5pm.[4]
Preparation
It can be formed by many methods, including combustion of sulfur is burnt in a deficiency oxygen. It arises by oxidizing sulfur with copper oxide:[5]
- 3/4 S8 + 3 CuO → 3 CuS + S2O + SO2
Other routes include the reaction of thionyl chloride with silver sulfide:
- SOCl2 + Ag2S → 2 AgCl + S2O
It also arises via thermal decomposition of sulfur dioxide ina glow discharge.[6]
Disulfur monoxide forms a yellow solution in carbon tetrachloride.[5] The solid can be obtained at liquid nitrogen temperatures, often appearing dark colored owing to impurities. On decomposition at room temperature it forms SO2 via the formation of polysulfur oxides.[6]
Discovery
Disulfur monoxide was first produced by P. W. Schenk in 1933[3] with a glow discharge though sulfur vapour and sulfur dioxide. He discovered that the gas could survive for hours at single digit pressures of mercury in clean glass, but decomposed near 30mm Hg Schenk assigned the formula as SO and called it sulfur monoxide. In 1940 K Kondrat'eva and V Kondrat'ev proposed the formula as S2O2, disulfur dioxide. In 1956, D. J. Meschi and R. J. Myers established the formula as S2O.[7]
Natural occurrence
Desulfovibrio desulfuricans is claimed to produce S2O.[8] S2O can be found coming from volcanoes on Io. It can form from 1 to 6% when hot 100 bar S2 and SO2 gas erupts from volcanoes. It is believed that Pele on Io is surrounded by solid S2O.[9]
Properties
Condensed solid S2O displays absorption bands at 420 and 530 nm. These are likely to be due to S3 and S4.[10]
The microwave spectrum of S2O has the following rotational parameters: A=41915.44, B=5059.07, and C=4507.19 MHz.[11]
In the ultraviolet S2O has absorption bands at 3235 and 3278 Å.[12]
The bond angle SSO is 109°.[12]
Reactions
A self decomposition of S2O can form trithio-ozone (S3) and SO2. Also 5,6-di-tert-butyl-2,3,7-trithiabicyclo[2.2.1]hept-5-ene 2-endo-7-endo-dioxide when heated can form S2O.[13] It reacts with diazoalkanes to form dithiirane 1-oxides.[14]
Disulfur monoxide is a ligand bound to transition metals. These are formed by oxidation peroxide oxidation of a disulfur ligands. Excessive oxygen can yield a dioxygendisulfur ligand, which can be reduced in turn with triphenylphosphine. Examples are: [Ir(dppe)2S2O]+, OsCl(NO)(PPh3)2S2O, NbCl(η-C5H5)2S2O, Mn(CO)2(η-C5Me5)S2O, Re(CO)2(η-C5Me5)S2O, Re(CO)2(η-C5H5)S2O.[15]
The molybdenum compound Mo(CO)2(S2CNEt2)2 reacts with elemental sulfur and air to form a compound Mo2(S2O)2(S2CNEt2)4.[15] Another way to form these complexes is to combine sulfonyliminooxo-λ4-sulfurane (OSNSO2.R) complexes with hydrogen sulfide.[15] Complexes formed in this way are: IrCl(CO)(PPh3)2S2O; Mn(CO)2(η-C5H5)S2O. With hydrosulfide and a base followed by oxygen, OsCl(NO)(PPh3)2S2O can be made.[15]
References
- ^ a b c d "Disulfur monoxide". NIST. 2008.
- ^ B Hapke and F Graham (May 1989). "Spectral properties of condensed phases of disulfur monoxide, polysulfur oxide, and irradiated sulfur". Icarus. 79 (1): 47. Bibcode:1989Icar...79...47H. doi:10.1016/0019-1035(89)90107-3.
- ^ a b R. Steudel: Sulfur-Rich Oxides SnO and SnO2" in Elemental Sulfur und Sulfur-Rich Compounds II, Steudel, R., 2003, Springer, Berlin-Heidelberg. ISBN 9783540449515
- ^ Meschi, D.J.; Myers R.J. (1959). "The microwave spectrum, structure, and dipole moment of disulfur monoxide". Journal of Molecular Spectroscopy. 3 (1–6): 405–416. Bibcode:1959JMoSp...3..405M. doi:10.1016/0022-2852(59)90036-0.
{{cite journal}}: Cite has empty unknown parameter:|quotes=(help) - ^ a b Satyanarayana, S. R.; A. R. Vasudeva Murthy (1964). "Reactions with Disulphur monoxide Solutions Obtained by the Reduction of Cupric Oxide by Elemental Sulphur" (PDF). Proceedings of the Indian Academy of Sciences Section A. 59 (4).
- ^ a b Cotton and Wilkinson (1966). Advanced Inorganic Chemistry A Comprehensive Treatise. p. 540.
- ^ David J. Meschi and Rollie J. Myers (30 July 1956). "Disulfur Monoxide. I. Its Identification as the Major Constituent in Schenk's "Sulfur Monoxide"". Journal of the American Chemical Society. 78 (24): 6220. doi:10.1021/ja01605a002.
- ^ Iverson, WP (26 May 1967). "Disulfur monoxide: production by Desulfovibrio". Science. 156 (3778): 1112–4. Bibcode:1967Sci...156.1112I. doi:10.1126/science.156.3778.1112. PMID 6024190.
- ^ Mikhail Yu. Zolotov and Bruce Fegley (9 March 1998). "Volcanic Origin of Disulfur Monoxide (S2O) on Io" (PDF). Icarus. 133 (2): 293. Bibcode:1998Icar..133..293Z. doi:10.1006/icar.1998.5930.
- ^ Cook, Robert L; Winnewisser, Gisbert; Lindsey, D.C (May 1973). "The centrifugal distortion constants of disulfur monoxide". Journal of Molecular Spectroscopy. 46 (2): 276–284. doi:10.1016/0022-2852(73)90042-8.
- ^ a b Hallin, K-E. J.; Merer, A. J.; Milton, D. J. (November 1977). "Rotational analysis of bands of the 3400 Å system of disulphur monoxide (S2O)". Canadian Journal of Physics. 55 (21): 1858–1867. doi:10.1139/p77-226.
- ^ Nakayama J; Aoki, S; Takayama, J; Sakamoto, A; Sugihara, Y; Ishii, A (28 July 2004). "Reversible disulfur monoxide (S2O)-forming retro-Diels-Alder reaction. disproportionation of S2O to trithio-ozone (S3) and sulfur dioxide (SO2) and reactivities of S2O and S3". Journal of the American Chemical Societ. 126 (29): 9085–93. doi:10.1021/ja047729i. PMID 15264842.
- ^ A Ishii; Kawai, T; Tekura, K; Oshida, H; Nakayama, J (18 May 2001). "A Convenient Method for the Generation of a Disulfur Monoxide Equivalent and Its Reaction with Diazoalkanes to Yield Dithiirane 1-Oxides". Angew Chem Int Ed Engl. 40 (10): 1924–1926. doi:10.1002/1521-3773(20010518)40:10<1924::AID-ANIE1924>3.0.CO;2-F. PMID 11385674.
- ^ a b c d F G A Stone (1994-03-07). Advances in Organometallic Chemistry, Volume 36. p. 168. ISBN 978-0-12-031136-1.
