Charge transfer properties of Tröger base derivatives.

Two triarylamine centers bridged through an aliphatic bridge feature unexpected charge transfer properties, bearing an important electronic coupling between them in the absence of a π linker; EPR, electrochemistry, electronic spectroscopy and first principles molecular calculations are combined to study the electronic structure of this compound.

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. Intermediate [Fe(III)(CN)(5)L](2-) complexes (L = NH(3), H(2)O) form dinuclear cyano-bridged mixed-valent species, affording a catalytic substitution of the L ligands promoted by [Fe(II)(CN)(5)L](3-). Free or bound NH(2)OCH(3) may act as reductants of [Fe(III)(CN)(5)L](2-), thus regenerating active sites. At increasing concentrations of NH(2)OCH(3) a coordinated diazene species emerges, [Fe(II)(CN)(5)N(2)H(2)](3-), which is consumed by the oxidizing CH(3)O(•), giving N(2) and CH(3)OH. Another side reaction forms [Fe(II)(CN)(5)N(O)CH(3)](3-), an intermediate containing the nitrosomethane ligand, which is further oxidized to the nitroprusside ion, [Fe(II)(CN)(5)NO](2-). The latter is a final oxidation product with a significant conversion of the initial [Fe(II)(CN)(5)H(2)O](3-) complex. The side reaction partially blocks the Fe(II)-aqua active site, though complete inhibition is not achieved because the radical path evolves faster than the formation rates of the Fe(II)-NO(+) bonds.

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). The progress of the addition process of HS(-) into the bound NO(+) ligand was monitored by stopped-flow UV/Vis/EPR and FTIR spectroscopy, mass spectrometry, and chemical analysis. Theoretical calculations were employed for the characterization of the initial adducts and reaction intermediates. The shapes of the absorbance-time curves at 535-575 nm depend on the pH and concentration ratio of the reactants, R=[HS(-)]/[NP]. The initial adduct [Fe(CN)(5)N(O)SH](3-) (AH, λ(max) ≈570 nm) forms in the course of a reversible process, with k(ad)=190±20 M(-1)s(-1) , k(-ad)=0.3±0.05 s(-1) . Deprotonation of AH (pK(a)=10.5±0.1, at 25.0 °C, I=1 M), leads to [Fe(CN)(5)N(O)S](4-) (A, λ(max)=535 nm, ε=6000±300 M(-1) cm(-1) ). [Fe(CN)(5)NO](.)(3-) and HS(2)(.)(2-) radicals form through the spontaneous decomposition of AH and A. The minor formation of the [Fe(CN)(5)NO](3-) ion equilibrates with [Fe(CN)(4)NO](2-) through cyanide labilization, and generates the "g=2.03" iron-dinitrosyl, [Fe(NO)(2)(SH)(2)](-) , which is labile toward NO release. Alternative nucleophilic attack of HS(-) on AH and A generates the reactive intermediates [Fe(CN)(5)N(OH)(SH)(2)](3-) and [Fe(CN)(5)N(OH)(S)(SH)](4-) , respectively, which decompose through multielectronic nitrosyl reductions, leading to NH(3) and hydrogen disulfide, HS(2)(-) . N(2)O is also produced at pH≥11. Biological relevance relates to the role of NO, NO(-) , and other bound intermediates, eventually able to be released to the medium and rapidly trapped by substrates. Structure and reactivity comparisons of the new nitrososulfide ligands with free and bound nitrosothiolates are provided.

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. Different N(2)/N(2)O ratios obtained with these three porphyrinates strongly suggest distinctive mechanistic scenarios: while [Fe(III)(TEPyP)](5+) and [Fe(III)(MP11)] formed unknown steady-state porphyrinic intermediates in the presence of HA, [Fe(III)(TPPS)](3-) led to the well characterized soluble intermediate, [Fe(II)(TPPS)NO](4-). Free-radical formation was only evidenced for [Fe(III)(TEPyP)](5+), as a consequence of a metal centered reduction. We discuss the catalytic pathways of HA disproportionation on the basis of the distribution of gaseous products, free radicals formation, the nature of porphyrinic intermediates, the Fe(II)/Fe(III) redox potential, the coordinating capabilities of each complex, and the kinetic analysis. The absence of NO(2)(-) revealed either that no HAO-like activity was operative under our reaction conditions, or that NO(2)(-), if formed, was consumed in the reaction milieu.

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-). [Fe(II)(CN)(5)(HNO)](3-) is the first non-heme iron-nitroxyl complex prepared in aqueous solution that is reversibly redox-active under biologically relevant conditions.

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)). With CH(3)N(H)OH, bound nitrosomethane, CH(3)NO, has been characterized by UV-visible and IR spectroscopies. The mechanism is discussed on the basis of common and differential features with respect to the disproportionation of hydroxylamine catalyzed by the same Fe-fragment.

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 7.1-9.3, 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-]x[MeN(H)OH]x[OH-], with kexp=1.6+/-0.2x10(5) M(-2) s(-1), at 25.0 degrees C, and DeltaH#=34+/-3 kJ mol(-1), DeltaS#=-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 SNP, the precursor complex reacts through a competitive one-electron-transfer path, forming the [Fe(CN)5NO]3- ion 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.

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)].3H(2)O as a precursor of the catalyst, [Fe(II)(CN)(5)H(2)O](3)(-). The oxidation products are N(2), N(2)O, and NO(+) (bound in the nitroprusside ion, NP), and NH(3) is the reduction product. The yields of N(2)/N(2)O increase with pH and with the concentration of NH(2)OH. Fast regime conditions involve a chain process initiated by the NH(2) radical, generated upon coordination of NH(2)OH to [Fe(II)(CN)(5)H(2)O](3)(-). NH(3) and nitroxyl, HNO, are formed in this fast process, and HNO leads to the production of N(2), N(2)O, and NP. An intermediate absorbing at 440 nm is always observed, whose formation and decay depend on the medium conditions. It was identified by UV-vis, RR, and (15)NMR spectroscopies as the diazene-bound [Fe(II)(CN)(5)N(2)H(2)](3)(-) ion and is formed in a competitive process with the radical path, still under the fast regime. At high pH's or NH(2)OH concentrations, an inhibited regime is reached, with slow production of only N(2) and NH(3). The stable red diazene-bridged [(NC)(5)FeHN=NHFe(CN)(5)](6)(-) ion is formed at an advanced degree of NH(2)OH consumption.

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 1.00 +/- 0.04 x 107 M-1 s-1. As well as resulting in a versatile method for obtaining ferrous nitrosyl porphyrins, the reaction points at ferric porphyrins as efficient nitroxyl traps and provides a tool to model nitroxyl reactivity toward hemeproteins.

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. The reaction of 1,2-Me(2)Hz follows a different route, characterized by azomethane formation (MeNNMe), full reduction of nitrosyl to NH(3), and intermediate detection of [Fe(CN)(5)NO](3)(-). In the above reactions, [Fe(CN)(5)H(2)O](3)(-) was always a product, allowing the system to proceed catalytically for nitrite reduction, an issue relevant in relation to the behavior of the nitrite and nitric oxide reductase enzymes. The mechanism comprises initial reversible adduct formation through the binding of the nucleophile to the N-atom of nitrosyl. The adducts decompose through OH(-) attack giving the final products, without intermediate detection. Rate constants for the adduct-formation steps (k = 0.43 M(-)(1) s(-)(1), 25 degrees C for Hz) decrease with methylation by about an order of magnitude. Among the different systems studied, one-, two-, and multielectron reductions of bound NO(+) are analyzed comparatively, with consideration of the role of NO, HNO (nitroxyl), and hydroxylamine as bound intermediates. A DFT study (B3LYP) of the reaction profile allows one to characterize intermediates in the potential hypersurface. These are the initial adducts, as well as their decomposition products, the eta(1)- and eta(2)-linkage isomers of N(2)O.