Nitrosonium

Nitrosonium
Names
	Systematic IUPAC name Oxidonitrogen(1+)
	Other names Nitrosonium; Iminooxidanium
Identifiers
CAS Number	14452-93-8;
3D model (JSmol)	Interactive image;
Abbreviations	NO(+)
ChEBI	CHEBI:29120;
ChemSpider	76569;
Gmelin Reference	456
PubChem CID	84878;
	InChI InChI=1S/NO/c1-2/q+1 Key: KEJOCWOXCDWNID-UHFFFAOYSA-N;
	SMILES N#[O+];
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	Infobox references

Short description: Diatomic cation

The nitrosonium ion is NO+
, in which the nitrogen atom is bonded to an oxygen atom with a bond order of 3, and the overall diatomic species bears a positive charge. It can be viewed as nitric oxide with one electron removed. This ion is usually obtained as the following salts: NOClO
4, NOSO
4H (nitrosylsulfuric acid, more descriptively written ONSO
3OH) and NOBF
4. The ClO−
4 and BF−
4 salts are slightly soluble in acetonitrile CH
3CN. NOBF₄ can be purified by sublimation at 200–250 °C and 0.01 mmHg (1.3 Pa).

NO+
is isoelectronic with CO, CN−
and N
2. It arises via protonation of nitrous acid:

HONO + H⁺ ⇌ NO⁺ + H₂O

Chemical properties

Hydrolysis

NO+
reacts readily with water to form nitrous acid:

NO⁺ + H
2O → HONO + H⁺

For this reason, nitrosonium compounds must be protected from water or even moist air. With base, the reaction generates nitrite:

NO⁺ + 2 NaOH → NaNO
2 + Na⁺ + H
2O

As a diazotizing agent

NO+
reacts with aryl amines, ArNH
2, to give diazonium salts, ArN+
2. The resulting diazonium group is easily displaced (unlike the amino group) by a variety of nucleophiles.

Reaction of nitrosonium with aniline to form a diazonium salt

As an oxidizing agent

NO+
, e.g. as NOBF
4, is a strong oxidizing agent:^[2]

vs. ferrocene/ferrocenium, [NO]+
in CH
2Cl
2 solution has a redox potential of 1.00 V (or 1.46–1.48 V vs SCE),
vs. ferrocene/ferrocenium, [NO]+
in CH
3CN solution has a redox potential of 0.87 V vs. (or 1.27–1.25 V vs SCE).

NOBF
4 is a convenient oxidant because the byproduct NO is a gas, which can be swept from the reaction using a stream of N
2. Upon contact with air, NO forms NO
2, which can cause secondary reactions if it is not removed. NO
2 is readily detectable by its characteristic orange color.

Nitrosylation of arenes

Electron-rich arenes are nitrosylated using NOBF₄.^[3] One example involves anisole:

CH₃OC₆H₅ + NOBF₄ → CH₃OC₆H₄NO + HBF₄

Nitrosonium, NO+
, is sometimes confused with nitronium, NO+2, the active agent in nitrations. These species are quite different, however. Nitronium is a more potent electrophile than is nitrosonium, as anticipated by the fact that the former is derived from a strong acid (nitric acid) and the latter from a weak acid (nitrous acid).

As a source of nitrosyl complexes

Main page: Chemistry:Metal nitrosyl complex

NOBF₄ reacts with some metal carbonyl complexes to yield related metal nitrosyl complexes.^[4] One must be careful that [NO]⁺ is transferred vs. electron transfer (see above).

(C₆Et₆)Cr(CO)₃ + NOBF₄ → [(C₆Et₆)Cr(CO)₂(NO)]BF₄ + CO

References

↑ Nomenclature of Inorganic Chemistry : IUPAC Recommendations 2005 (Red Book). Cambridge: The Royal Society of Chemistry. 2005. p. 315. ISBN 978-0-85404-438-2. https://archive.org/details/nomenclatureinor2005conn.
↑ N. G. Connelly, W. E. Geiger (1996). "Chemical Redox Agents for Organometallic Chemistry". Chem. Rev. 96 (2): 877–910. doi:10.1021/cr940053x. PMID 11848774.
↑ E. Bosch and J. K. Kochi. "Direct Nitrosation of Aromatic Hydrocarbons and Ethers with the Electrophilic Nitrosonium Cation". Journal of Organic Chemistry, 1994, volume 59, pp. 5573–5586.
↑ T. W. Hayton, P. Legzdins, W. B. Sharp. "Coordination and Organometallic Chemistry of Metal-NO Complexes". Chemical Reviews 2002, volume 102, pp. 935–991.

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[iupac2005-1] Nomenclature of Inorganic Chemistry : IUPAC Recommendations 2005 (Red Book). Cambridge: The Royal Society of Chemistry. 2005. p. 315. ISBN 978-0-85404-438-2. https://archive.org/details/nomenclatureinor2005conn.

[2] N. G. Connelly, W. E. Geiger (1996). "Chemical Redox Agents for Organometallic Chemistry". Chem. Rev. 96 (2): 877–910. doi:10.1021/cr940053x. PMID 11848774.

[3] E. Bosch and J. K. Kochi. "Direct Nitrosation of Aromatic Hydrocarbons and Ethers with the Electrophilic Nitrosonium Cation". Journal of Organic Chemistry, 1994, volume 59, pp. 5573–5586.

[4] T. W. Hayton, P. Legzdins, W. B. Sharp. "Coordination and Organometallic Chemistry of Metal-NO Complexes". Chemical Reviews 2002, volume 102, pp. 935–991.

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