INSTITUTO DE QUIMICA, FISICA DE LOS MATERIALES, MEDIOAMBIENTE Y ENERGIA
Unidad Ejecutora - UE
Nitrosation of N-methylhydroxylamine by nitroprusside. A kinetic and mechanistic study
M. M. GUTIÉRREZ, G. B. ALLUISETTI, J. A. OLABE, V. T. AMOREBIETA
JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS
Lugar: Londres; Año: 2008 p. 5025 - 5025
The kinetics of the reaction between aqueous solutions of Na2[Fe(CN)5NO].2H2O (sodium pentacyanonitrosylferrate(II), nitroprusside, SNP) and MeN(H)OH (N-methylhydroxylamine, MeHA) has been studied by means of UV-vis spectroscopy, using complementary solution techniques: FTIR/ATR, EPR, mass spectrometry and isotopic labeling (15NO), in the pH range 7.1-9.3, I = 1 M (NaCl). The main products were N-methyl-N-nitrosohydroxylamine (MeN(NO)OH) and [Fe(CN)5H2O]3−, characterized as the [Fe(CN)5(pyCONH2)]3− complex (pyCONH2 = isonicotinamide). No reaction occurred with Me2NOH (N,N-dimethylhydroxylamine, Me2HA) as nucleophile. The rate law was: R = kexp [Fe(CN)5NO2−] [MeN(H)OH] [OH−], with kexp = 1.6 ± 0.2 ´ 105 M−2 s−1, at 25.0 ºC, and DH# = 34 ± 3 kJ mol−1, DS# = −32 ± 11 J K−1 mol−1, at pH 8.0. The proposed mechanism involves the formation of a precursor associative complex between SNP and MeHA, followed by an OH−-assisted reversible formation of a deprotonated adduct, [Fe(CN)5(N(O)NMeOH)]3−, and rapid dissociation of MeN(NO)OH. In excess of SNP, the precursor complex reacts through a competitive one-electron-transfer path, forming the [Fe(CN)5NO]3− ion and with slow production of small quantities of N2O. The stoichiometry and mechanism of the main adduct-formation path are similar to those previously reported for hydroxylamine (HA) and related nucleophiles. The nitrosated product, MeN(NO)OH, decomposes thermally at physiological temperatures, slowly yielding NO.