Nitrosonium s. Nitrosyl

A. R. Butler, F. W. Fhtney, D. L. H. Williams, NO, Nitrosonium Ions, Nitroxide Ions, Nitrosothiols and Iron-Nitrosyls in Biology A Chemist s Perspective , Trends Pharmacol. Sci. 1995, 16, 18-22. 

Butler, A., Flitney, FW, and Williams, DL. 1995. NO, nitrosonium ions, nitroxide ions, nitrosothiols and iron-nitrosyls in biology a chemist s perspective. Trends Pharmacol Sci 16 18-22. 

Alkylation of thioamides with Meerwein s reagent (trialkoxonium fluoroborate) proceeds via a thioiminoester and subsequent base hydrolysis with sodium carbonate (equation 32). For the synthesis of 2-pyridones from 2-thiopyridones, chloroacetic acid has been used. ° Mild reaction conditions are provided by nitrosyl species which are derived from a variety of reagents excess NaNOa/HCP in aqueous medium, nitrosonium tetrafluoroborate in dichloromethane, dinitrogen tetroxide in acetonitrile at low temperature and f-butyl thionitrate. ... 

Here again measurements are confined to the nitrosyl pentacyanides. There is a large literature on the ESR spectrum of K3[Cr(NO)(CN)5] 48, 68, 71 and references therein) and some disagreement as to the interpretation, but the formulation of the complex as a nitrosonium coordination compound is upheld by the results, and this is also the conclusion reached from ESR studies on the isoelectronic complex K2[Mn(NO)(CN)5] 68). In the case of [Fe(NO)(CN)s], a species not yet isolated from solution, the delocalization of the unpaired electron onto the ligand appears to be such that the complex may almost be regarded as an example of nitric oxide donating an electron pair only to iron(II) 45). A study of C hyperfine interaction in the ion has recently been made 15). 

Haim and Taube reacted [CoN3(NH3)s]2+ with nitrosyl chloride in water S which led to the formation of [Co(NH3)5(H20)]3+, dinitrogen, and nitrous oxide. [Co(N3)Cl(en)2]+ underwent a similar reaction in water56 57 with formation of [CoCl(en)2(H20)]2+. Following this early work, several methods were developed that similarly employed azide ligand elimination as the result of redox transformations in non-aqueous solvents. The complex [CoN3(NH3)s]2+ and nitrosonium salts were reacted in trimethylphosphate, tetramethylene sulfone,59 or organonitriles with the formation of the... 

---