Nitrosyl chloride: Difference between revisions
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==Reactions== |
==Reactions== |
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Revision as of 17:21, 15 April 2021
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| Names | |
|---|---|
| IUPAC name
Nitrosyl chloride[citation needed]
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| Identifiers | |
3D model (JSmol)
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| ChemSpider | |
| ECHA InfoCard | 100.018.430 |
| EC Number |
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| E number | E919 (glazing agents, ...) |
| MeSH | nitrosyl+chloride |
PubChem CID
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| RTECS number |
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| UNII | |
| UN number | 1069 |
CompTox Dashboard (EPA)
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| Properties | |
| NOCl | |
| Molar mass | 65.459 g mol−1 |
| Appearance | Yellow gas |
| Density | 2.872 mg mL−1 |
| Melting point | −59.4 °C (−74.9 °F; 213.8 K) |
| Boiling point | −5.55 °C (22.01 °F; 267.60 K) |
| Reacts | |
| Structure | |
| Dihedral, digonal | |
| Hybridisation | sp2 at N |
| 1.90 D | |
| Thermochemistry | |
Std molar
entropy (S⦵298) |
261.68 J K−1 mol−1 |
Std enthalpy of
formation (ΔfH⦵298) |
51.71 kJ mol−1 |
| Hazards | |
| NFPA 704 (fire diamond) | |
| Safety data sheet (SDS) | inchem.org |
| Related compounds | |
Related compounds
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Nitrosyl chloride is the chemical compound with the formula NOCl. It is a yellow gas that is most commonly encountered as a decomposition product of aqua regia, a mixture of hydrochloric acid and nitric acid. It is a strong electrophile and oxidizing agent. It is sometimes called Tilden's reagent.
Structure and synthesis
The molecule is bent. A double bond exists between N and O (distance = 1.16 Å) and a single bond between N and Cl (distance = 1.96 Å). The O–N–Cl angle is 113°.[1]
Production
Since nitrosyl chloride is chemically simple and thermally stable, it can be produced in many ways.
- Combining nitrosylsulfuric acid and HCl affords the compound. This method is used industrially.[2]
- HCl + NOHSO4 → H2SO4 + NOCl
- A more convenient laboratory method involves the (reversible) dehydration of nitrous acid by HCl[3]
- HNO2 + HCl → H2O + NOCl
- Michael Faraday prepared nitrosyl chloride by reacting palladium with aqua regia:
- Pd + HNO3 + 3 HCl → PdCl2 + 2 H2O + NOCl
- NOCl forms by the direct combination of chlorine and nitric oxide; This reaction reverses above 100 °C.
- Cl2 + 2 NO → 2NOCl
- Another method of producing nitrosyl chloride is by direct union of the elements at 400 °C, although there is some regression as above.
- N2 + O2 + Cl2 → 2 NOCl ⇌ 2 NO + Cl2
Occurrence in aqua regia
NOCl also arises from the combination of hydrochloric and nitric acids according to the following reaction:[4]
- HNO3 + 3 HCl → Cl2 + 2 H2O + NOCl
In nitric acid, NOCl is readily oxidized into nitrogen dioxide. The presence of NOCl in aqua regia was described by Edmund Davy in 1831.Cite error: A <ref> tag is missing the closing </ref> (see the help page).
Nitrosyl chloride is used to prepare metal nitrosyl complexes. With molybdenum hexacarbonyl, NOCl gives the dinitrosyldichloride complex:[5]
- Mo(CO)6 + 2 NOCl → MoCl2(NO)2 + 6 CO
It dissolves platinum:[6]
- Pt + 6 NOCl → (NO+)2[PtCl6]2- + 4 NO
Applications in organic synthesis
Aside from its role in the production of caprolactam, NOCl finds some other uses in organic synthesis. It adds to alkenes to afford α-chloro oximes.[7] The addition of NOCl follows the Markovnikov rule. Ketenes also add NOCl, giving nitrosyl derivatives:
- H2C=C=O + NOCl → ONCH2C(O)Cl
Epoxides react with NOCl to give an α-chloronitritoalkyl derivatives. In the case of propylene oxide, the addition proceeds with high regiochemistry:[8]
It converts amides to N-nitroso derivatives.[9] NOCl converts some cyclic amines to the alkenes. For example, aziridine reacts with NOCl to give ethene, nitrous oxide and hydrogen chloride.
Industrial applications
NOCl and cyclohexane react photochemically to give cyclohexanone oxime hydrochloride. This process exploits the tendency of NOCl to undergo photodissociation into NO and Cl radicals. The oxide is converted to caprolactam, a precursor to Nylon-6.[2]
Safety
Nitrosyl chloride is very toxic and irritating to the lungs, eyes, and skin.
References
- ^ Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
- ^ a b Ritz, Josef; Fuchs, Hugo; Kieczka, Heinz; Moran, William C. Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a05_031. ISBN 978-3527306732.
- ^ Morton, J. R.; Wilcox, H. W. (1953). "Nitrosyl Chloride". Inorganic Syntheses. Inorganic Syntheses. Vol. 48. p. 52. doi:10.1002/9780470132357.ch16. ISBN 9780470132357.
- ^ Beckham, L. J.; Fessler, W. A.; Kise, M. A. (1951). "Nitrosyl Chloride". Chemical Reviews. 48 (3): 319–396. doi:10.1021/cr60151a001. PMID 24541207.
- ^ Johnson, B. F. G.; Al-Obadi, K. H. (1970). "Dihalogenodinitrosylmolybdenum and Dihalogenodinitrosyltungsten". Inorg. Synth. 12: 264–266. doi:10.1002/9780470132432.ch47.
- ^ Moravek, Richard T. (1986). "Nitrosyl Hexachloroplatinate(IV)". Inorganic Syntheses. 24: 217–220. doi:10.1002/9780470132555.ch63.
- ^ Ohno, M.; Naruse, N.; Terasawa, I. (1969). "7-Cyanoheptanal". Org. Synth. 49: 27. doi:10.15227/orgsyn.049.0027.
- ^ Malinovskii, M. S.; Medyantseva, N. M. (1953). "Olefin Oxides. IX. Condensation of Olefin Oxides with Nitrosyl Chloride". Zhurnal Obshchei Khimii. 23: 84-6. (translated from Russian)
- ^ Van Leusen, A. M.; Strating, J. (1977). "p-Tolylsulfonyldiazomethane". Org. Synth. 57: 95. doi:10.15227/orgsyn.057.0095.
External links
Media related to Nitrosyl chloride at Wikimedia Commons
