Disproportionation of O-methylhydroxylamine catalyzed by aquapentacyanoferrate(II).

The aquapentacyanoferrate(II) ion, [Fe(II)(CN)(5)H(2)O](3-), catalyzes the disproportionation reaction of O-methylhydroxylamine, NH(2)OCH(3), with stoichiometry 3NH(2)OCH(3) → NH(3) + N(2) + 3CH(3)OH. Kinetic and spectroscopic evidence support an initial N coordination of NH(2)OCH(3) to [Fe(II)(CN)(5)H(2)O](3-) followed by a homolytic scission leading to radicals [Fe(II)(CN)(5)(•)NH(2)](3-) (a precursor of Fe(III) centers and bound NH(3)) and free methoxyl, CH(3)O(•), thus establishing a radical path leading to N-methoxyamino ((•)NHOCH(3)) and 1,2-dimethoxyhydrazine, (NHOCH(3))(2). The latter species is moderately stable and proposed to be the precursor of N(2) and most of the generated CH(3)OH.

Addition and redox reactivity of hydrogen sulfides (H2S/HS⁻) with nitroprusside: new chemistry of nitrososulfide ligands.

The nitroprusside ion [Fe(CN)(5)NO](2-) (NP) reacts with excess HS(-) in the pH range 8.5-12.5, in anaerobic medium ("Gmelin" reaction).

Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds.

The reactions of hydroxylamine (HA) with several water-soluble iron(III) porphyrinate compounds, namely iron(III) meso-tetrakis-(N-ethylpyridinium-2yl)-porphyrinate ([Fe(III)(TEPyP)](5+)), iron(III) meso-tetrakis-(4-sulphonatophenyl)-porphyrinate ([Fe(III)(TPPS)](3-)), and microperoxidase 11 ([Fe(III)(MP11)]) were studied for different [Fe(III)(Porph)]/[HA] ratios, under anaerobic conditions at neutral pH. Efficient catalytic processes leading to the disproportionation of HA by these iron(III) porphyrinates were evidenced for the first time. As a common feature, only N(2) and N(2)O were found as gaseous, nitrogen-containing oxidation products, while NH(3) was the unique reduced species detected.

Three redox states of nitrosyl: NO+, NO*, and NO-/HNO interconvert reversibly on the same pentacyanoferrate(II) platform.

Not so elusive: [Fe(II)(CN)(5)(HNO)](3-) has been characterized spectroscopically after the two-electron reduction of nitroprusside (see scheme). The complex is stable at pH 6, slowly decomposing to [Fe(CN)(6)](4-) and N(2)O. It is deprotonated at increasing pH value with oxidation of bound NO(-) to [Fe(II)(CN)(5)(NO)](3-).

Catalytic disproportionation of N-alkylhydroxylamines bound to pentacyanoferrates.

The substituted hydroxylamines, CH(3)N(H)OH (N-methylhydroxylamine) and (CH(3))(2)NOH (N,N-dimethylhydroxylamine), disproportionate catalytically to the corresponding alkylamines and oxidation products, only in the presence of [Fe(CN)(5)H(2)O](3-). Substitution kinetic measurements suggest an initial coordination step to Fe(ii). Two parallel N- and O-coordination modes are considered with the subsequent formation of Fe(iii), free aminyl (RNCH(3)) and nitroxide (RN(CH(3))O) radicals (R = H, CH(3)).

Nitrosation of N-methylhydroxylamine by nitroprusside. A kinetic and mechanistic study.

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.

Metal-catalyzed anaerobic disproportionation of hydroxylamine. Role of diazene and nitroxyl intermediates in the formation of N2, N2O, NO+, and NH3.

The catalytic disproportionation of NH(2)OH has been studied in anaerobic aqueous solution, pH 6-9.3, at 25.0 degrees C, with Na(3)[Fe(CN)(5)NH(3)].

Fast nitroxyl trapping by ferric porphyrins.

Iron(II) porphyrin nitrosyl complexes are obtained in high yields from the reaction of iron(III) porphyrins with the nitroxyl donors sodium trioxodinitrate and toluensulfohydroxamic acid. The reaction was found to proceed both in organic solvents and in aqueous media from iron(III) (meso-tetraphenyl) porphyrinate ([FeIII(TPP)]+) and iron(III) meso-tetrakis (4-sulfonatophenyl) porphyrinate ([FeIII(TPPS)]3-) or iron(III) protoporphyrin IX, respectively. The kinetic rate constant for the reaction of ([FeIII(TPPS)]3-) with sodium trioxodinitrate (kon) was estimated to be 1.

The electrophilic reactions of pentacyanonitrosylferrate(II) with hydrazine and substituted derivatives. Catalytic reduction of nitrite and theoretical prediction of eta(1)-, eta(2)-N(2)O bound intermediates.

The electrophilic reactivity of the pentacyanonitrosylferrate(II) ion, [Fe(CN)(5)NO](2)(-), toward hydrazine (Hz) and substituted hydrazines (MeHz, 1,1-Me(2)Hz, and 1,2-Me(2)Hz) has been studied by means of stoichiometric and kinetic experiments (pH 6-10). The reaction of Hz led to N(2)O and NH(3), with similar paths for MeHz and 1,1-Me(2)Hz, which form the corresponding amines. A parallel path has been found for MeHz, leading to N(2)O, N(2), and MeOH.