Sulfur monoxide

Sulfur monoxide is an inorganic compound with formula Template:Chem2. 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.

Structure and bonding

The SO molecule has a triplet ground state similar to O₂ and S₂, that is, each molecule has two unpaired electrons.<ref name = greenwood>Template:Greenwood&Earnshaw</ref> 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).<ref name = greenwood />

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.<ref>Template:Cite journal</ref>

Production and reactions

The SO molecule is thermodynamically unstable, converting initially to S₂O₂.<ref name = greenwood/> 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:<ref>Template:Cite journal</ref>

C₂H₄SO → C₂H₄ + SO

Yields directly from an episulfoxide are poor, and improve only moderately when the carbons are sterically shielded.<ref>Template:Cite journal</ref> A much better approach decomposes a diaryl cyclic trisulfide oxide, C₁₀H₆S₃O, produced from thionyl chloride and the dithiol.<ref>Template:Cite journal</ref>

SO inserts into alkenes, alkynes and dienes producing thiiranes, molecules with three-membered rings containing sulfur.<ref>Template:Cite journal</ref>

Sulfur monoxide may form transiently during the metallic reduction of thionyl bromide.<ref name=Sulf>Template:Cite book</ref>

Generation under extreme conditions

In the laboratory, sulfur monoxide can be produced by treating sulfur dioxide with sulfur vapor in a glow discharge.<ref name = greenwood /> It has been detected in single-bubble sonoluminescence of concentrated sulfuric acid containing some dissolved noble gas.<ref>Template:Cite journal</ref>

Benner and Stedman developed a chemiluminescence detector for sulfur via the reaction between sulfur monoxide and ozone:<ref>Template:Cite journal</ref>

SO + O₃ → SO₂* + O₂

SO₂* → SO₂ + hν

Occurrence

Ligand for transition metals

As a ligand SO can bond in a number different ways:<ref>Template:Cite journal</ref><ref>Template:Cite encyclopedia</ref>

• a terminal ligand, with a bent M−O−S arrangement, for example with titanium oxyfluoride<ref>Template:Cite journal</ref>
• 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.<ref>Template:Cite journal</ref>

Astrochemistry

Sulfur monoxide has been detected around Io, one of Jupiter's moons, both in the atmosphere<ref>Template:Cite journal</ref> and in the plasma torus.<ref>Template:Cite journal</ref> It has also been found in the atmosphere of Venus,<ref>Template:Cite journal</ref> in Comet Hale–Bopp,<ref>Template:Cite journal</ref> in 67P/Churyumov–Gerasimenko,<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> and in the interstellar medium.<ref>Template:Cite journal</ref>

On Io, SO is thought to be produced both by volcanic and photochemical routes. The principal photochemical reactions are proposed as follows:<ref>Template:Cite journal</ref>

O + S₂ → S + SO

SO₂ → SO + O

Sulfur monoxide has been found in NML Cygni.<ref name="Marvel1996">Template:Cite book</ref>

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.<ref>Template:Cite journal</ref>

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.<ref>Template:Cite journal</ref>

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

Disulfur dioxide

File:Disulfur-dioxide-2D-dimensions.png

The structure of disulfur dioxide, S₂O₂

File:Disulfur-dioxide-3D-vdW-A.png

A space-filling model of the disulfur dioxide molecule

{{#invoke:Labelled list hatnote|labelledList|Main article|Main articles|Main page|Main pages}} SO converts to disulfur dioxide (S₂O₂).<ref name =lovas>Template:Cite journal</ref> Disulfur dioxide is a planar molecule with C_2v 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.<ref name = lovas />