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'''Disulfur monoxide''' or '''sulfur suboxide''' is an unstable gas being a compound of [[sulfur]] and oxygen with formula S<sub>2</sub>O. It is one of the [[lower sulfur oxides]]. It is a colourless gas. It can be formed by reacting [[thionyl chloride]] with [[silver sulfide]]:
'''Disulfur monoxide''' or '''sulfur suboxide''' is an [[inorganic compound]] with formula S<sub>2</sub>O. 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.<ref name=Steudel>R. Steudel: Sulfur-Rich Oxides S<sub>n</sub>O and S<sub>n</sub>O<sub>2</sub>" in Elemental Sulfur und Sulfur-Rich Compounds II, Steudel, R., 2003, Springer, Berlin-Heidelberg. ISBN 9783540449515</ref> 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.<ref>{{cite journal
⚫
| quotes = | last =Meschi | first =D.J. | authorlink = |author2=Myers R.J.| year = 1959| title = The microwave spectrum, structure, and dipole moment of disulfur monoxide| journal = Journal of Molecular Spectroscopy| volume = 3| issue =1–6 | pages =405–416 | publisher = | doi = 10.1016/0022-2852(59)90036-0| url = |bibcode = 1959JMoSp...3..405M }}</ref>


==Preparation==
⚫
:SOCl<sub>2</sub> + Ag<sub>2</sub>S <big>→</big> 2[[silver chloride|AgCl]] + S<sub>2</sub>O.
⚫
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]]:<ref name="Satyanarayana64">{{cite journal|last=Satyanarayana|first=S. R.|author2=A. R. Vasudeva Murthy|year=1964|title=Reactions with Disulphur monoxide Solutions Obtained by the Reduction of Cupric Oxide by Elemental Sulphur|journal=Proceedings of the Indian Academy of Sciences Section A|volume=59|issue=4|url=http://eprints.iisc.ernet.in/28079/1/32.pdf}}</ref>


:3/4 S<sub>8</sub> + 3 CuO → 3 CuS + S<sub>2</sub>O + SO<sub>2</sub>
This is done under low pressure and high temperature.<ref>{{cite journal|title=Ullmann's Encyclopedia of Industrial Chemistry|doi=10.1002/14356007.a25_623|chapter=Sulfur Halides|year=2000|last1=Lauss|first1=Hans-Dietrich|last2=Steffens|first2=Wilfried|isbn=3-527-30673-0}}</ref> Another way to form it is via a [[glow discharge]] in [[sulfur dioxide]].<ref name=candw/> The arrangement of atoms is SSO in a bent form. The angle formed at the central sulfur atom is 117.88°. The sulfur to sulfur bond length is 188.4pm, and the length of the oxygen bond is 146.5pm.<ref>{{cite journal
⚫
| quotes = | last =Meschi | first =D.J. | authorlink = |author2=Myers R.J.| year = 1959| title = The microwave spectrum, structure, and dipole moment of disulfur monoxide| journal = Journal of Molecular Spectroscopy| volume = 3| issue =1–6 | pages =405–416 | publisher = | doi = 10.1016/0022-2852(59)90036-0| url = |bibcode = 1959JMoSp...3..405M }}</ref> It can form an orange red condensate at liquid nitrogen temperatures. On decomposition at room temperature it forms SO<sub>2</sub> and [[polysulfur oxide]].<ref name=candw>{{cite book|title=Advanced Inorganic Chemistry A Comprehensive Treatise|author=Cotton and Wilkinson|year=1966|page=540}}</ref>


Other routes include the reaction of thionyl chloride with silver sulfide:
⚫
It is the base oxide for [[thiosulfurous acid]].<ref>{{cite book|title=Objective Chemistry For Iit Entrance|author=Alok Mittal|page=13|url=http://books.google.com.au/books?id=SzN1oCapakAC|isbn=978-81-224-1365-6|date=2002-01-01}}</ref> The formal oxidation state for sulfur is +1; sulfur plays two different roles in the molecule, however.
⚫
:SOCl<sub>2</sub> + Ag<sub>2</sub>S → 2 AgCl + S<sub>2</sub>O


It also arises via thermal decomposition of [[sulfur dioxide]] ina [[glow discharge]].<ref name=candw/>
⚫
Disulfur monoxide is also formed in a small amount when sulfur is burnt in insufficient oxygen. It is also formed in part by heating sulfur with cupric oxide.<ref name="Satyanarayana64">{{cite journal|last=Satyanarayana|first=S. R.|author2=A. R. Vasudeva Murthy|year=1964|title=Reactions with Disulphur monoxide Solutions Obtained by the Reduction of Cupric Oxide by Elemental Sulphur|journal=Proceedings of the Indian Academy of Sciences Section A|volume=59|issue=4|url=http://eprints.iisc.ernet.in/28079/1/32.pdf}}</ref>

⚫
==Discovery==
Disulfur monoxide forms a yellow solution in carbon tetrachloride.<ref name="Satyanarayana64"/> The solid can be obtained at liquid nitrogen temperatures, often appearing dark colored owing to impurities. On decomposition at room temperature it forms SO<sub>2</sub> via the formation of polysulfur oxides.<ref name=candw>{{cite book|title=Advanced Inorganic Chemistry A Comprehensive Treatise|author=Cotton and Wilkinson|year=1966|page=540}}</ref>
⚫
The gas was first produced by P. W. Schenk in 1933 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 when the pressure went up to 30mm of mercury. However he believed that the formula was SO and called it [[sulfur monoxide]]. In 1940 K Kondrat'eva and V Kondrat'ev became convinced that the formula was S<sub>2</sub>O<sub>2</sub>, [[disulfur dioxide]]. However all were wrong until in 1956, David J. Meschi and Rollie J. Myers proved the formula was S<sub>2</sub>O.<ref>{{cite journal|journal=Journal of the American Chemical Society|title=Disulfur Monoxide. I. Its Identification as the Major Constituent in Schenk's "Sulfur Monoxide"|author=David J. Meschi and Rollie J. Myers|date=30 July 1956|volume=78|issue=24|page=6220|doi=10.1021/ja01605a002|url=http://pubs.acs.org/doi/abs/10.1021/ja01605a002}}</ref>

⚫
===Discovery===
⚫
Disulfur monoxide was first produced by P. W. Schenk in 1933<ref name=Steudel/> 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 S<sub>2</sub>O<sub>2</sub>, [[disulfur dioxide]]. In 1956, D. J. Meschi and R. J. Myers established the formula as S<sub>2</sub>O.<ref>{{cite journal|journal=Journal of the American Chemical Society|title=Disulfur Monoxide. I. Its Identification as the Major Constituent in Schenk's "Sulfur Monoxide"|author=David J. Meschi and Rollie J. Myers|date=30 July 1956|volume=78|issue=24|page=6220|doi=10.1021/ja01605a002|url=http://pubs.acs.org/doi/abs/10.1021/ja01605a002}}</ref>
⚫
<!--It is the base oxide for [[thiosulfurous acid]].<ref>{{cite book|title=Objective Chemistry For Iit Entrance|author=Alok Mittal|page=13|url=http://books.google.com.au/books?id=SzN1oCapakAC|isbn=978-81-224-1365-6|date=2002-01-01}}</ref> The formal oxidation state for sulfur is +1; sulfur plays two different roles in the molecule, however.-->


==Natural occurrence==
==Natural occurrence==
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==Reactions==
==Reactions==
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>

Disulfur monoxide can be a [[ligand]] bound to [[transition metal]]s. These are formed by oxidation with dioxygen for a disulfur ligand complex. Excessive oxygen can yield a dioxygendisulfur ligand, which can be reduced in turn with [[triphenylphosphine]]. Examples are: ''[Ir(dppe)<sub>2</sub>S<sub>2</sub>O]<sup>+</sup>'', ''OsCl(NO)(PPh<sub>3</sub>)<sub>2</sub>S<sub>2</sub>O'', ''NbCl(η-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>S<sub>2</sub>O'', ''Mn(CO)<sub>2</sub>(η-C<sub>5</sub>Me<sub>5</sub>)S<sub>2</sub>O'', ''Re(CO)<sub>2</sub>(η-C<sub>5</sub>Me<sub>5</sub>)S<sub>2</sub>O'', ''Re(CO)<sub>2</sub>(η-C<sub>5</sub>H<sub>5</sub>)S<sub>2</sub>O''.<ref name=aioc>{{cite book|url=http://books.google.com.au/books?id=SMsrNhK_5y4C|page=168|title=Advances in Organometallic Chemistry, Volume 36|author=F G A Stone|isbn=978-0-12-031136-1|date=1994-03-07}}</ref>


More complex nucleations occur with transition metal ligand combinations. The molybdenum compound Mo(CO)<sub>2</sub>(S<sub>2</sub>CNEt<sub>2</sub>)<sub>2</sub> reacts with elemental sulfur and air to form a compound Mo<sub>2</sub>(S<sub>2</sub>O)<sub>2</sub>(S<sub>2</sub>CNEt<sub>2</sub>)<sub>4</sub>.<ref name=aioc/> Another way to form these complexes is to combine [[sulfonyliminooxosulfurane|sulfonyliminooxo-λ<sup>4</sup>-sulfurane]] (OSNSO<sub>2</sub>.R) complexes with [[hydrogen sulfide]].<ref name=aioc/> Complexes formed in this way are: IrCl(CO)(PPh<sub>3</sub>)<sub>2</sub>S<sub>2</sub>O; Mn(CO)<sub>2</sub>(η-C5H5)S<sub>2</sub>O. With hydrosulfide and a base followed by oxygen, OsCl(NO)(PPh<sub>3</sub>)<sub>2</sub>S<sub>2</sub>O can be made.<ref name=aioc/>
Disulfur monoxide is a [[ligand]] bound to [[transition metal]]s. 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)<sub>2</sub>S<sub>2</sub>O]<sup>+</sup>'', ''OsCl(NO)(PPh<sub>3</sub>)<sub>2</sub>S<sub>2</sub>O'', ''NbCl(η-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>S<sub>2</sub>O'', ''Mn(CO)<sub>2</sub>(η-C<sub>5</sub>Me<sub>5</sub>)S<sub>2</sub>O'', ''Re(CO)<sub>2</sub>(η-C<sub>5</sub>Me<sub>5</sub>)S<sub>2</sub>O'', ''Re(CO)<sub>2</sub>(η-C<sub>5</sub>H<sub>5</sub>)S<sub>2</sub>O''.<ref name=aioc>{{cite book|url=http://books.google.com.au/books?id=SMsrNhK_5y4C|page=168|title=Advances in Organometallic Chemistry, Volume 36|author=F G A Stone|isbn=978-0-12-031136-1|date=1994-03-07}}</ref>


The molybdenum compound Mo(CO)<sub>2</sub>(S<sub>2</sub>CNEt<sub>2</sub>)<sub>2</sub> reacts with elemental sulfur and air to form a compound Mo<sub>2</sub>(S<sub>2</sub>O)<sub>2</sub>(S<sub>2</sub>CNEt<sub>2</sub>)<sub>4</sub>.<ref name=aioc/> Another way to form these complexes is to combine [[sulfonyliminooxosulfurane|sulfonyliminooxo-λ<sup>4</sup>-sulfurane]] (OSNSO<sub>2</sub>.R) complexes with [[hydrogen sulfide]].<ref name=aioc/> Complexes formed in this way are: IrCl(CO)(PPh<sub>3</sub>)<sub>2</sub>S<sub>2</sub>O; Mn(CO)<sub>2</sub>(η-C5H5)S<sub>2</sub>O. With hydrosulfide and a base followed by oxygen, OsCl(NO)(PPh<sub>3</sub>)<sub>2</sub>S<sub>2</sub>O can be made.<ref name=aioc/>
Disulfur monoxide forms a yellow solution in carbon tetrachloride.<ref name="Satyanarayana64"/>


==References==
==References==

Revision as of 15:40, 11 October 2014

Disulfur monoxide
Structure of S2O
solid ball model of S2O
Names
Other names
sulfur suboxide; Sulfuroxide;
Identifiers
ChemSpider
  • [1]: InChI=1S/OS2/c1-3-2
    Key: TXKMVPPZCYKFAC-UHFFFAOYSA-N
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]

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.[10] It reacts with diazoalkanes to form dithiirane 1-oxides.[11]

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.[12]

The molybdenum compound Mo(CO)2(S2CNEt2)2 reacts with elemental sulfur and air to form a compound Mo2(S2O)2(S2CNEt2)4.[12] Another way to form these complexes is to combine sulfonyliminooxo-λ4-sulfurane (OSNSO2.R) complexes with hydrogen sulfide.[12] 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.[12]

References

  1. ^ a b c d "Disulfur monoxide". NIST. 2008.
  2. ^ 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.
  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
  4. ^ 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)
  5. ^ 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).
  6. ^ a b Cotton and Wilkinson (1966). Advanced Inorganic Chemistry A Comprehensive Treatise. p. 540.
  7. ^ 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.
  8. ^ 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.
  9. ^ 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.
  10. ^ 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.
  11. ^ 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.
  12. ^ 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.
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