Nitrosyl chloride
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| Names | |
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| IUPAC name
Nitrosyl chloride[1]
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| Identifiers | |
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3D model (JSmol)
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| MeSH | nitrosyl+chloride |
PubChem CID
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| UN number | 1069 |
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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) | Page Template:NFPA 704 diamond/styles.css has no content. |
| 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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Template:Chembox Footer/trackingTemplate:Short description
Nitrosyl chloride is the chemical compound with the formula NOCl. It is a yellow gas that is commonly encountered as a component of aqua regia, a mixture of 3 parts concentrated hydrochloric acid and 1 part of concentrated nitric acid. It is a strong electrophile and oxidizing agent. It is sometimes called Tilden's reagent, after William A. Tilden, who was the first to produce it as a pure compound.[2]
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°.[3]
Production
Nitrosyl chloride can be produced in many ways.
- Combining nitrosylsulfuric acid and HCl affords the compound. This method is used industrially.[4]
- HCl + NOHSO4 → H2SO4 + NOCl
- A more convenient laboratory method involves the (reversible) dehydration of nitrous acid by HCl[5]
- HNO2 + HCl → H2O + NOCl
- By the direct combination of chlorine and nitric oxide; This reaction reverses above 100 °C.
- Cl2 + 2 NO → 2 NOCl
- By reduction of nitrogen dioxide with hydrogen chloride:[6]
- 2NO2 + 4 HCl → 2NOCl + 2H2O + Cl2
Occurrence in aqua regia
NOCl also arises from the combination of hydrochloric and nitric acids according to the following reaction:[7]
- HNO3 + 3 HCl → 2[Cl] + 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.[8]
Reactions
NOCl behaves as an electrophile and an oxidant in most of its reactions. With halide acceptors it gives nitrosonium salts, and synthesis of nitrosonium tetrachloroferrate is typically performed in liquid NOCl:Lua error in package.lua at line 80: module 'Module:Footnotes/anchor_id_list' not found.
- NOCl + FeCl3 → [NO]+[FeCl4]−
In a related reaction, sulfuric acid gives nitrosylsulfuric acid, the mixed acid anhydride of nitrous and sulfuric acid:
- ClNO + H2SO4 → ONHSO4 + HCl
NOCl reacts with silver thiocyanate to give silver chloride and the pseudohalogen nitrosyl thiocyanate:
- ClNO + AgSCN → AgCl + ONSCN
Similarly, it reacts with silver cyanide to give nitrosyl cyanide.[9]
Nitrosyl chloride is used to prepare metal nitrosyl complexes. With molybdenum hexacarbonyl, NOCl gives the dinitrosyldichloride complex:[10]
- Mo(CO)6 + 2 NOCl → MoCl2(NO)2 + 6 CO
It dissolves platinum:[11]
- 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.[12] The addition of NOCl follows the Markovnikov rule. Ketenes also add NOCl, giving nitrosyl derivatives:
- H2C=C=O + NOCl → ONCH2C(O)Cl
Carbonyl compounds enolize; and then NOCl attacks the nucleophilic end of the alkene to give a vicinal keto- or aldo-oxime.Lua error in package.lua at line 80: module 'Module:Footnotes/anchor_id_list' not found.
Epoxides react with NOCl to give an α-chloronitritoalkyl derivatives. In the case of propylene oxide, the addition proceeds with high regiochemistry:[13]
It converts amides to N-nitroso derivatives.[14] 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 cyclohexanone oxime is converted to caprolactam, a precursor to nylon-6.[4]Lua error in package.lua at line 80: module 'Module:Footnotes/anchor_id_list' not found.
Historical importance
Before the advent of modern spectroscopic methods for chemical analysis, informative chemical degradation and structure elucidation required the characterization of the individual components of various extracts. Notably, the aforementioned introduction of nitrosyl chloride by Tilden in 1875, as a reagent for producing crystalline derivatives of terpenes, e.g. α-pinene from oil of turpentine allowed investigators to readily distinguish one terpene from another.:[15]
Safety
Nitrosyl chloride is very toxic and irritating to the lungs, eyes, and skin.
References
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- ^ Nitrosyl chloride from PubChem
- ^ Page Module:Citation/CS1/styles.css has no content.Tilden, William A. (1874). "XXXII.—On aqua regia and the nitrosyl chlorides". J. Chem. Soc. 27: 630–636. doi:10.1039/JS8742700630.
- ^ Page Module:Citation/CS1/styles.css has no content.Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
- ^ a b Script error: No such module "Template wrapper".
- ^ Page Module:Citation/CS1/styles.css has no content.Morton, J. R.; Wilcox, H. W.; Moellerf, Therald; Edwards, Delwin C. (1953). "Nitrosyl Chloride". In Bailar, John C. Jr (ed.). Inorganic Syntheses. Vol. 4. McGraw-Hill. p. 48. doi:10.1002/9780470132357.ch16. ISBN 9780470132357.
{{cite book}}: ISBN / Date incompatibility (help) - ^ Page Module:Citation/CS1/styles.css has no content.Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 456. doi:10.1016/C2009-0-30414-6. ISBN 978-0-08-037941-8.
- ^ Page Module:Citation/CS1/styles.css has no content.Beckham, L. J.; Fessler, W. A.; Kise, M. A. (1951). "Nitrosyl Chloride". Chemical Reviews. 48 (3): 319–396. doi:10.1021/cr60151a001. PMID 24541207.
- ^ Page Module:Citation/CS1/styles.css has no content.Edmund Davy (1830–1837). "On a New Combination of Chlorine and Nitrous Gas". Abstracts of the Papers Printed in the Philosophical Transactions of the Royal Society of London. 3: 27–29. JSTOR 110250.
- ^ Page Module:Citation/CS1/styles.css has no content.Kirby, G. W. (1977). "Tilden Lecture. Electrophilic C-Nitroso Compounds". Chemical Society Reviews. 6: 1. doi:10.1039/CS9770600001.
- ^ Page Module:Citation/CS1/styles.css has no content.Johnson, B. F. G.; Al-Obadi, K. H. (1970). "Dihalogenodinitrosylmolybdenum and Dihalogenodinitrosyltungsten". Inorganic Syntheses. Vol. 12. pp. 264–266. doi:10.1002/9780470132432.ch47. ISBN 9780470132432.
{{cite book}}:|journal=ignored (help) - ^ Page Module:Citation/CS1/styles.css has no content.Moravek, Richard T. (1986). "Nitrosyl Hexachloroplatinate(IV)". Inorganic Syntheses. Vol. 24. pp. 217–220. doi:10.1002/9780470132555.ch63. ISBN 9780470132555.
- ^ Page Module:Citation/CS1/styles.css has no content.Ohno, M.; Naruse, N.; Terasawa, I. (1969). "7-Cyanoheptanal". Org. Synth. 49: 27. doi:10.15227/orgsyn.049.0027.
- ^ Page Module:Citation/CS1/styles.css has no content.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)
- ^ Page Module:Citation/CS1/styles.css has no content.Van Leusen, A. M.; Strating, J. (1977). "p-Tolylsulfonyldiazomethane". Org. Synth. 57: 95. doi:10.15227/orgsyn.057.0095.
- ^ Page Module:Citation/CS1/styles.css has no content.Hanson, J.S. (2001). "The development of strategies for terpenoid structure determination". Natural Product Reports. 18 (6): 607–617. doi:10.1039/b103772m. PMID 11820760.
Bibliography
- Page Module:Citation/CS1/styles.css has no content.Williams, D. L. H. (1988). Nitrosation. Cambridge, UK: Cambridge University. ISBN 0-521-26796-X.
External links
- Page Template:Sister-inline/styles.css has no content.Script error: No such module "Sister project logo". Media related to Script error: No such module "Commons link". at Wikimedia Commons
