Nitroprusside Nitrosation

Nitrosyl complexes, in which Vno > 1886 cm or Fnq > 13.8 mdyn/A, usually react as electrophilic nitrosating agents so that the ligand can be considered NO [26]. Nucleophilic attack on the nitrosyl nitrogen is a common reaction encountered in the chemistry of nitroprusside and the rates and activation parameters for a number of different nucleophiles are listed in Table 3. Hydr-oxylamine adducts to nitroprusside via a rate law that is first order in the complex, the ligand and hydroxide (k = 4.5 x 10 M s ). 

The nitrosation mechanism of aliphatic amines by metal nitrosyl complexes was studied with various secondary amines and one primary amine (ethylamine) using pentacyanonitrosylferrate (sodium nitroprusside). Very little mechanistic information is available for reactions with other metal nitrosyl complexes (see also Sects. 2.3, 4.3, and 7.2). 

Mechanistic investigations of Casado et al. (1983 b, 1985 b) and Butler et al. (1984) with secondary alkylamines show that the rates of these nitrosations are of first-order in the concentration of nitroprusside ion and of first- or second-order in the amine concentration. Normally, both terms are present but, sometimes, depending... 

Product distribution in alkaline nitrosations with nitroprusside ion is significantly different from that in acidic solution (McGarvie and Kimura, 1986 see Sect. 7.4). 

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