Nitrosonium Explained

The nitrosonium ion is, 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:, (nitrosylsulfuric acid, more descriptively written) and . The and salts are slightly soluble in acetonitrile . NOBF4 can be purified by sublimation at 200–250 °C and 0.01mmHg.[1]

Synthesis and spectroscopy

is isoelectronic with CO, and . It arises via protonation of nitrous acid:

HONO + H+ NO+ + H2O

In its infrared spectrum of its salts, νNO is a strong peak in the range 2150-2400 cm−1.[2]

Chemical properties

Hydrolysis

reacts readily with water to form nitrous acid:

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

As a diazotizing agent

reacts with aryl amines,, to give diazonium salts, . The resulting diazonium group is easily displaced (unlike the amino group) by a variety of nucleophiles.

As an oxidizing agent

, e.g. as, is a strong oxidizing agent:[3]

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

Nitrosylation of arenes

Electron-rich arenes are nitrosylated using NOBF4.[4] One example involves anisole:

CH3OC6H5 + NOBF4 → CH3OC6H4NO + HBF4Nitrosonium,, is sometimes confused with nitronium, NO, 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

See main article: Metal nitrosyl complex. NOBF4 reacts with some metal carbonyl complexes to yield related metal nitrosyl complexes.[5] In some cases, [NO]+ does not bind the metal nucleophile but acts as an oxidant.

(C6Et6)Cr(CO)3 + NOBF4 → [(C<sub>6</sub>Et<sub>6</sub>)Cr(CO)<sub>2</sub>(NO)]BF4 + CO

See also

Notes and References

  1. Olah . George A. . Surya Prakash . G. K. . Wang . Qi . Li . Xing-ya . Surya Prakash . G. K. . Hu . Jinbo . Nitrosonium Tetrafluoroborate . Encyclopedia of Reagents for Organic Synthesis . 15 October 2004 . rn058.pub2 . 10.1002/047084289X.rn058.pub2. 0471936235 .
  2. 10.1039/JR9630003557 . 670. The Infrared Spectrum of the Nitrosonium Ion . 1963 . Sharp . D. W. A. . Thorley . J. . Journal of the Chemical Society (Resumed) . 3557 .
  3. N. G. Connelly, W. E. Geiger . Chemical Redox Agents for Organometallic Chemistry . . 1996 . 96 . 877–910 . 10.1021/cr940053x . 11848774 . 2.
  4. E.. Bosch. J. K.. Kochi. Direct Nitrosation of Aromatic Hydrocarbons and Ethers with the Electrophilic Nitrosonium Cation. Journal of Organic Chemistry. 1994. 59. 19 . 5573–5586. 10.1021/jo00098a015.
  5. T. W. Hayton, P. Legzdins, W. B. Sharp. "Coordination and Organometallic Chemistry of Metal-NO Complexes". Chemical Reviews 2002, volume 102, pp. 935–991.