Wikipedia

Disiloxane

This article is about a specific compound. For the class of compounds, see siloxane.

Disiloxane has the chemical formula Si
2H
6O. It is the simplest known siloxane with hydrogen only R groups. The molecule contains six equivalent Si−H bonds and two equivalent Si−O bonds. Disiloxane exists as a colorless, pungent gas under standard conditions. However, it is generally safe for human use as evidence in its widespread use in cosmetics. It is also commonly known as disilyl ether, disilyl oxide, and perhydrodisiloxane

Disiloxane
Structural formula of disiloxane with explicit hydrogens
Ball-and-stick model of the disiloxane molecule
Names
IUPAC name
Disiloxane
Other names
Disilyl ether

Disilyl oxide
Hexahydrodisiloxane
Perhydrodisiloxane
Silyl ether

Silyl oxide
Identifiers
3D model (JSmol)
Abbreviations DS

DSE
DSO

ChEBI
ChemSpider
1206
MeSH Disiloxane
  • InChI=1S/H6OSi2/c2-1-3/h2-3H3 checkY
    Key: KPUWHANPEXNPJT-UHFFFAOYSA-N checkY
  • [SiH3]O[SiH3]
Properties
H6OSi2
Molar mass 78.217 g·mol−1
Appearance Colorless gas
Boiling point −15.2 °C (4.6 °F; 257.9 K)
0.24 D
Structure
Orthorhombic
Pmm2
Bent
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
2
4
1
Related compounds
Related compounds
 Dimethyl ether

Disilane
Silane
Silanol
Trisilane

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Structure

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Disiloxane has a simple structure that consists of a siloxane bond (Si−O−Si) and hydrogen R groups.

The structure of disiloxane has been studied by a variety of spectroscopic methods such as electron diffraction,[1] X-ray crystallography,[2] dipole moment, and nuclear magnetic resonance spectroscopy. Due to their unusual nature, the Si−O−Si bond angles are commonly studied. These bonds typically exhibit angles that are larger than average, around 130 to 160 degrees, and larger bond lengths are not uncommon.[3] For example, in the solid state at a temperature of 108 K, disiloxane itself has an Si−O−Si bond angle of 142°.[2] In contrast, the C−O−C bond angle in the carbon analogue of disiloxane, dimethyl ether, is 111°.[4]

The unusual bond angle in disiloxane has been attributed primarily to negative hyperconjugation between oxygen p orbitals and silicon–carbon σ* antibonding orbitals, p(O) → σ*(Si􏰉−R), a form of π backbonding. A secondary and much smaller contribution to the silicon–oxygen bond in disiloxanes involves π backbonding from oxygen 2p orbitals to silicon 3d orbitals, p(O) → d(Si). Because of this interaction, the Si−O bonds can exhibit some partial double bond behavior and the oxygen atoms are much less basic than in the carbon analogue, dimethyl ether.[5]

In addition to studies of bond angles, vibrational analyses have also been done to determine the symmetry elements of disiloxane. IR and Raman spectroscopy have been used to propose a point group of D3d.[citation needed]

While disiloxane itself has a bent molecular geometry at oxygen, the related compound hexaphenyldisiloxane, Ph3Si−O−SiPh3, has an Si−O−Si angle of 180°.[6]

Synthesis

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Synthesis of disiloxane is typically done by taking a hydrosilane species with a substituent leaving group and reacting it with water to produce silanol. The silanol is then reacted with itself to produce the final disiloxane through dehydrative coupling. This is shown in the reactions below:

H3SiX + H2O → H3SiOH + HX (first step)

2 H3SiOH → H3SiOSiH3 + H2O (second step)

Other methods of synthesis involve the use of gold on carbon as a catalyst for the reaction carried out in water as well as InBr3- catalyzed oxidation of hydrosilanes.

Uses

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Disiloxanes can be used as sealants for construction, paints, inks, and coatings, cosmetics, mechanical fluids, textile applications, and paper coatings.

Commercial use of disiloxane is common in cosmetics. It is commonly found in products such as sunscreen, moisturizer, hair spray, eye liner, body spray, nail polish, makeup remover, and conditioner. The properties that disiloxane exhibits in these products include fast drying, oil reducing, moisturizing, skin conditioning, and defoaming agent (preventing formation of foam).

Disiloxanes have been approved as teen and child safe. Siloxanes of many kinds are found to be extremely safe for topical use but can be dangerous if ingested in large quantities.

Variations

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The term disiloxane is commonly used to refer to structures that exhibit much more complex R groups than hydrogen. The most common molecule that makes use of this naming is hexamethyldisiloxane which replaces the hydrogen groups with methyl groups. Other common variations include the use of disiloxanes as bridges and spacers in larger compounds such as polymers.

References

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  1. ^ Almenningen, A.; Bastiansen, O.; Ewing, V.; Hedberg, Kenneth; Trætteberg, M. (1963). "The Molecular Structure of Disiloxane, (SiH3)2O". Acta Chem. Scand. 17: 2455–2460. doi:10.3891/acta.chem.scand.17-2455.
  2. ^ a b Barrow, M. J.; Ebsworth, E. A. V.; Harding, M. M. (1979). "The crystal and molecular structures of disiloxane (at 108 K) and hexamethyldisiloxane (at 148 K)". Acta Crystallogr. B. 35 (9): 2093–2099. Bibcode:1979AcCrB..35.2093B. doi:10.1107/S0567740879008529.
  3. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 342–344, 348–349. ISBN 978-0-08-037941-8.
  4. ^ Vojinović, Krunoslav; Losehand, Udo; Mitzel, Nobert W. (2004). "Dichlorosilane–dimethyl ether aggregation: a new motif in halosilane adduct formation". Dalton Trans. (16): 2578–2581. doi:10.1039/B405684A. PMID 15303175.
  5. ^ Dankert, Fabian; von Hänisch, Carsten (2021). "Siloxane Coordination Revisited: Si􏰉−O Bond Character, Reactivity and Magnificent Molecular Shapes". Eur. J. Inorg. Chem. 2021 (29): 2907–2927. doi:10.1002/ejic.202100275. S2CID 239645449.
  6. ^ Glidewell, C.; Liles, D. C. (1978). "The crystal and molecular structure of oxobis[triphenylsilicon(IV)]". Acta Crystallogr. B. 34 (1): 124–128. Bibcode:1978AcCrB..34..124G. doi:10.1107/S0567740878002435. S2CID 98347658.
  1. Sawama, Y.; Masuda, M.; Yasukawa, N.; Nakatani, R.; Nishimura, S.; Shibata, K.; Yamada, T.; Monguchi, Y.; Suzuka, H.; Takagi, Y.; Sajiki, H. The Journal of Organic Chemistry2016, 81, 4190–4195.
  2. Disiloxane https://pubchem.ncbi.nlm.nih.gov/compound/Disiloxane (accessed Mar 23, 2018).
  3. Lassen, C.; Hansen, C.; Mikkelsen, S.; Maag, J. Siloxanes-Consumption, Toxicity, and Alternatives; Danish Ministry of the Environment, 2018.
  4. Lord, R.; Robinson, D.; Schumb, W. Journal of the American Chemical Society 1956, 78, 1327–1332.
  5. Varma, R.; MacDiarmid, A.; Miller, J. Inorganic Chemistry 1964, 3, 1754–1757.
  6. BOCK, H.; MOLLERE, P.; BECKER, G.; FRITZ, G. Chemischer Informationsdienst 1974, 5, 113–125.
  7. Disiloxane | H6OSi2 | ChemSpider http://www.chemspider.com/Chemical-Structure.109921.html (accessed Mar 23, 2018).
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