Low-temperature activation of nitrogen oxide on Cu-ZSM-5 catalysts

The adsorption and activation of NO molecules on Cu-ZSM-5 catalysts with different Cu/Al and Si/Al ratios (from 0.05 to 1.4 and from 17 to 45, respectively) subjected to different pretreatment was studied by ultraviolet-visible diffuse reflectance (UV-Vis DR). It was found that the amount of chemisorbed NO and the catalyst activity in NO decomposition increased with an increase in the Cu/Al ratio to 0.35–0.40. The intensity of absorption bands at 18400 and 25600 cm⁻¹ in the UV-Vis DR spectra increased symbatically. It was hypothesized that the adsorption of NO occurs at Cu⁺ ions localized in chain copper oxide structures with the formation of mono- and dinitrosyl Cu(I) complexes, and this process is accompanied by the Cu²⁺...Cu⁺ intervalence transfer band in the region of 18400 cm⁻¹. The low-temperature activation of NO occurs through the conversion of the dinitrosyl Cu(I) complex into the π-radical anion (N₂O₂)⁻ stabilized at the Cu²⁺ ion of the chain structure, [Cu²⁺-cis-(N₂O₂)⁻], by electron transfer from the Cu⁺ ion to the cis dimer (NO)₂. This complex corresponds to the L → M charge transfer band in the region of 25600 cm⁻¹. The subsequent destruction of the complex [Cu²⁺-cis-(N₂O₂)⁻] at temperatures of 150–300°C leads to the release of N₂O and the formation of the complex [Cu²⁺O⁻], which further participates in the formation of the nitrite-nitrate complexes [Cu²⁺(NO₂)⁻], [Cu²⁺(NO)(NO₂)⁻], and [Cu²⁺(NO₃)⁻] and NO decomposition products.     

Alkylation of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with alkyl halides and dimethyl sulfate

Salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides, RCH(OH)CH₂N(O)=NO⁻ M⁺ (R=Me, Prⁱ, or Bu^t; and M=Li, Na, K, Ag, NH₄, or Me₄N), were prepared. Their alkylation with alkyl halides R′X (X=Cl, Br, or I) and dimethyl sulfate was studied. Generally, alkylation afforded mixtures ofN-(β-hydroxyalkyl)-N′-alkoxydiazeneN-oxides RCH(OH)CH₂N(O)=NOR′ andO-alkyl-N-(β-hydroxyalkyl)-N-nitrosohydroxylamines RCH(OH)CH₂N(NO)OR′. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1996–2001, October, 1998.     

N<Subscript>2</Subscript>O Production by Nitrifying Biomass Under Anoxic and Aerobic Conditions

The capacity of nitrifying biomass, grown in biofilms or in suspension, to reduce NO₂ ^- and NO₃ ⁻ under anoxic conditions was tested in batch experiments. The estimated reduction rates were 5 and 25 mg N per gram volatile suspended solids (VSS) per day for nitrate and nitrite, respectively, in the case of the nitrifying biofilms. Activity tests carried out with successive feedings indicated that no acclimation of the biomass to the tested conditions occurred, as the obtained reduction rates remained almost constant. Another series of activity assays was carried out with nitrifying suspended biomass, and the reduction rates for nitrate and nitrite were 30.4 and 48.9 mg N per gram VSS per day, respectively. N₂O and N₂ were the final gaseous products, and their percentages depended on the source of nitrogen feed. The specific production of nitrous oxide during nitrification was investigated during continuous experiments in a biofilm airlift suspension reactor. Specific production rates up to 46 mg N₂O–N per gram VSS per day were measured. The percentage of N₂O produced represented up to 34.4% of the ammonia oxidized. Nitrite accumulation, low dissolved oxygen concentrations, and the presence of organic matter favored the production of nitrous oxide. N₂O gas was not detected during the oxidation of nitrite even when organic matter was present. To prevent N₂O gas production in nitrifying systems, the operation at low dissolved oxygen concentrations, nitrite presence, or organic matter content should be avoided.     

Novel ruthenium based electrocatalyst for the convenient reduction of nitrogen-nitrogen bonds in azide to ammonia in aqueous solution

The interaction of azide (N ₃ ⁻ ) ion, at pH 5.3 with [Ru^III(EDTA) (H₂O)]⁻ (EDTA = ethylenediaminetetraacetate) was studied in aqueous solution by polarography and cyclic voltammetry. The product, [Ru^III(EDTA)(N₃)]²⁻ showed a multi-electron reduction step, which is polarographically reversible but, cyclic voltammetrically irreversible, in the potential range − 0.1 to − 0.2 V vs SCE. This reduction step, which was different from the one-electron reduction step of [Ru^III(EDTA)(H₂O)]; (E^1/2 = −0.113V vs SCE) was assigned to the reduction of the coordinated azide ion to ammonia by the irreversible transfer of electrons from Hg-electrode via ruthenium metal. Azide, at pH 5.3, was reduced, electrolytically, for the first time, to ammonia at Hg-pool cathode mediated by [Ru^III(EDTA) (N₃)]²⁻. The turnover number with respect to the formation of ammonia (moles of ammonia per mole of ruthenium per hour) was obtained from the constant potential electrolysis data. On the basis of experimental observations, a probable mechanism has been proposed for the electrocatalytic reduction of azide to ammonia in aqueous solution.     

Preparation of a novel polymer gel electrolyte based on N-methyl-quinoline iodide and its application in quasi-solid-state dye-sensitized solar cell

Using poly(acrylonitrile-co-styrene) as polymer host, 1,2-propanediol carbonate, dimethyl carbonate and ethylene carbonate as mixture solvent, N-methyl-quinoline iodide and iodine as the source of I⁻/I₃ ⁻, a novel polymer gel electrolyte with ionic conductivity of 5.12 × 10⁻³ S· cm⁻¹ at 25°C was prepared by sol-gel and hydrothermal methods. Based on the polymer gel electrolyte, a quasi-solid-state dye-sensitized solar cell was fabricated. The solar cell possess better long-term stability and light-to-electrical energy conversion efficiency of 4.04% under irradiation of 100 mW· cm⁻². The influences of polymer host, solvent, N-methyl-quinoline iodide and temperature on ionic conductivity of the polymer gel electrolyte and the performance of the dye-sensitized solar cell was discussed.     

Thermal behaviour of nickel(II) sulphate,nitrate and halide complexes containing ammine and ethylenediamine as ligands

Thermal behaviour of nickel amine complexes containing SO₄ ²⁻, NO₃ ⁻, Cl⁻ and Br⁻ as counter ions and ammonia and ethylenediamine as ligands have been investigated using simultaneous TG/DTA coupled with mass spectroscopy (TG/DTA–MS). Evolved gas analyses detected various transient intermediates during thermal decomposition. The nickel ammonium sulphate complex produces NH, N, S, O and N₂ species. The nickel ammonium nitrate complex generated fragments like N, N₂, NO, O₂, N₂O, NH₂ and NH. The halide complexes produce NH₂, NH, N₂ and H₂ species during decomposition. The ligand ethylenediamine is fragmented as N₂/C₂H₄, NH₃ and H₂. The residue hexaamminenickel(II) sulphate produces NiO with crystallite size 50 nm. Hexaammine and tris(ethylenediamine)nickel(II) nitrate produce NiO in the range 25.5 nm and 23 nm, respectively. The halide complexes produce nano sized metallic nickel (20 nm) as the residue. Among the complexes studied, the nitrate containing complexes undergo simultaneous oxidation and reduction.     

A bimetallic cyano-bridged complex based on nickel(II) and pentacyanidonitrosylferrate(II) precursors: characterization, crystal structure, and magnetic properties

A heterobimetallic cyano-bridged 1D coordination polymer of the composition [Ni(baepn)(μ-NC)Fe(CN)₃(NO)(μ-CN)]_n·3H₂O has been synthesized by the reaction of nickel(II) nitrate hexahydrate, baepn (baepn = N, N′-bis(2-aminoethyl)-1,3-propanediamine), and sodium nitroprusside dihydrate in a methanol–water mixture. The complex was characterized by physicochemical and spectroscopic methods. The crystal structure was established by single-crystal X-ray diffraction analysis. It reveals cyano-bridged heterometallic chains consisting of alternating arrays of Ni(II) and Fe(II) atoms, both being embedded in distorted octahedral environments. Low-temperature susceptibility measurements show the presence of weak antiferromagnetic exchange interactions between paramagnetic Ni(II) centers (J = −0.46 cm⁻¹) through long diamagnetic [Fe(CN)₅(NO)]²⁻ bridges. Spin state of the iron atom was established by ⁵⁷Fe M?ssbauer spectroscopy.     

Nitrite formation in aerated aqueous azide solutions: A radiation chemical study

Gamma radiolysis of oxygenated 1–10 mM azide solutions was carried out at various pH values. In oxygenated 10 mM azide solutions, H₂O₂ and NO ₂ ⁻ were observed as radiolytic products while NH3 was not. The concentration of H₂O₂ reached its maximum level at a dose of 1 kGy, whereas NO ₂ ⁻ yield increased non-linearly beyond 2 kGy in this system. Both in aerated and oxygenated systems, G(NO ₂ ⁻ ) and G(H₂O₂) were found to vary with N ₃ ⁻ concentration. The yield of NO ₂ ⁻ was found to be dependent on both dose rate and pH. On pulse radiolysis, NO ₂ ⁻ was found as a radiolytic product in aerated 1 mM azide solution at pH 6.8. In this system the intermediate generated exhibits absorbance around 250 nm. The overall results obtained during the present study reveal that in presence of both reducing radical (mainly e _aq ⁻ ) and oxygen, N ₃ ⁻ produced an intermediate possibly NH₂O ₂ ^• radical, which is the prime source for NO ₂ ⁻ generation.     

Sensitive determination of nitric oxide in some rat tissues using polymer monolith microextraction coupled to high-performance liquid chromatography with fluorescence detection

A simple, sensitive, selective, and low-cost method is proposed for rapidly determining nitric oxide (NO) in some rat tissues. Polymer monolith microextraction (PMME) using a poly(methacrylic acid–ethylene glycol dimethacrylate) (MAA-EGDMA) monolithic column was combined with derivatization of NO using 1,3,5,7-tetramethyl-8-(3′,4′-diaminophenyl)-difluoroboradiaza-s-indacene (TMDABODIPY), and this was used to analyze the derivatives of NO by high-performance liquid chromatography (HPLC) with fluorescence detection at λ _ex/λ _em = 498/507 nm. The baseline separation of TMDABODIPY and its NO derivative is performed under simple conditions in which a C₁₈ column is used and eluted with 50 mmol L⁻¹ ethanolamine and methanol. The conditions for the extraction of NO derivatives were optimized. The limit of detection of NO was 2 × 10⁻¹² mol L⁻¹ (S/N = 3). The linearity range of the method was 9 × 10⁻¹¹−4.5 × 10⁻⁸ mol L⁻¹. The interday and intraday relative standard deviations were less than 5%. The proposed method was successfully applied to the determination of NO levels in some rat tissue samples including heart, kidney, and liver with recoveries varying from 87.1 to 95.2%.     

Mechanism of the reduction of molecular nitrogen to hydrazine by niobium (iii) hydroxide

The effect of the concentration of water on the rate of reduction of molecular nitrogen to hydrazine by niobium(iii) hydroxide in alkaline H₂O−MeOH and D₂O−MeOD mixtures was studied. In both cases, the reaction rate is maximum when [H₂O]=4 mol L⁻¹, and the inverse isotopic effect (K ^D/k ^H>1) is observed when [H₂O]<20 mol L⁻¹. Similar regularity was observed for the reaction of hydrogen elimination. It was found that HD is formed in the H₂O−MeOH system in the presence of D₂. The conclusion was made that the ratedetermining stage in hydrazine formation is the transfer of a hydride ion to the dinitrogen molecule coordinated to the binuclear Nb^III center. A kinetic scheme satisfactorily explaining the effect of the concentration of water ([H₂O]=1.5−49.0 mol L⁻¹) on the reaction rate constant was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1600–1604, September, 1997.     

Electrocatalytic oxidation of nitrite at a terpyridine manganese(II) complex modified carbon past electrode

A carbon past electrode modified with [Mn(H₂O)(N₃)(NO₃)(pyterpy)], ( \textpyterpy = 4￠- ( 4 - \textpyridyl ) - 2,2￠:\text6￠,\text2￠￠- \textterpyridine ) \left( {{\text{pyterpy}} = 4\prime - \left( {4 - {\text{pyridyl}}} \right) - 2,2\prime:{\text{6}}\prime,{\text{2}}\prime\prime - {\text{terpyridine}}} \right) complex have been applied to the electrocatalytic oxidation of nitrite which reduced the overpotential by about 120 mV with obviously increasing the current response. Relative standard deviations for nitrite determination was less than 2.0%, and nitrite can be determined in the ranges of 5.00 × 10⁻⁶ to 1.55 × 10⁻² mol L⁻¹, with a detection limit of 8 × 10⁻⁷ mol L⁻¹. The treatment of the voltammetric data showed that it is a pure diffusion-controlled reaction, which involves one electron in the rate-determining step. The rate constant k′, transfer coefficient α for the catalytic reaction, and diffusion coefficient of nitrite in the solution, D, were found to be 1.4 × 10⁻², 0.56× 10⁻⁶, and 7.99 × 10⁻⁶ cm² s⁻¹, respectively. The mechanism for the interaction of nitrite with the Mn(II) complex modified carbon past electrode is proposed. This work provides a simple and easy approach to detection of nitrite ion. The modified electrode indicated reproducible behavior, anti-fouling properties, and stability during electrochemical experiments, making it particularly suitable for the analytical purposes.     

Matrix IR-spectroscopic and quantum-chemical study of difluorostannylene complexation with dinitrogen

Complexes of difluorostannylene with dinitrogen of composition 1∶1 and 1∶2 were stabilized in Ar matrix (12 K) and characterized by IR spectra. The bands at 588, 565, and 583, 557 cm⁻¹, respectively, were assigned to these complexes. Potential energy surfaces of the systems SnF₂+N₂ and SnF₂+2N₂ were studied by theab initio MP2/3-21G(d2)//HF/3-21G(d2) method using the basis set including polarization functions at Sn, F, and N atoms. Equilibrium structures of the complexes haveC _s andC _2v symmetry and correspond to coordination of lone electron pairs of nitrogen molecules with vacant p-AO of the carbenic center. The calculated complexation energies are equal to 4.6 and 8.9 kcal mol⁻¹, respectively. Based on results of quantum-chemical calculations an interpretation of the IR spectra of the complexes was given and it was shown that cycloaddition of SnF₂ to a triple N≡N bond with formation ofcyclo-SnF₂N₂ is energetically unfavorable. The absorption band belonging to SiF₄·N₂ complex in Ar matrix was detected and assigned. Dedicated to the memory of Academician M. E. Vol'pin timed to his 75th birthday. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1087–1093, June, 1998.     

Determination of p-nitroaniline by the tartrate-acetone-Mn2+-KBrO3-H2SO4 double organic substrate oscillating system using non-equilibrium stationary state

This paper described the determination of p-nitroaniline in a double organic substrate oscillating system of tartrate-acetone-Mn²⁺-KBrO₃-H₂SO₄. Under the optimum conditions, temperature was chosen as a control parameter to design the bifurcation point and proposed a convenient method for determination of p-nitroaniline. Results showed that the system consisting of 3.5 mL 0.06 mol L⁻¹ tartrate, 4.0 mL 0.7 mol L⁻¹ H₂SO₄, 1.5 mL 1.5×10⁻⁴ mol L⁻¹ MnSO₄, 4.0 mL 0.4 mol L⁻¹ acetone and 7.0 mL 0.05 mol L⁻¹ KBrO₃ was very sensitive to the surrounding at 33.5°C. A good linear relationship between the potential difference and the negative logarithm concentration of p-nitroaniline was obtained to be in the range of 2.50×10⁻⁷∼3.75×10⁻⁵ mol L⁻¹ with a lower detection limit of 2.50×10⁻⁸ mol L⁻¹.      

Solvation Structure and Complexation of the Manganese(II) Ion in N,N-Dimethylpropionamide and N,N,N′,N′-Tetramethylurea Studied by Means of Titration Calorimetry and Raman Spectroscopy

Aprotic N,N-dimethylpropionamide (DMPA) and N,N,N′,N′-tetramethylurea (TMU) are both strong donor solvents and coordinate to metal ions through the carbonyl oxygen atom. These solvents show a different conformational aspect in the bulk phase, i.e., DMPA exists as either a planar cis or a nonplanar staggered conformer, while TMU exists in a single planar cis conformer. It has been established that the manganese(II) ion is solvated by five molecules in both solvents. Interestingly, although the planar cis conformer of DMPA is more favorable than the nonplanar staggered one in the bulk phase, the reverse is the case in the coordination sphere of the metal ion, i.e., a conformational change occurs upon solvation. To reveal the thermodynamic aspect of this conformational change, the complexation of Mn(II) with bromide ions in DMPA and TMU has been studied by titration calorimetry at 298 K. It was found that the Mn(II) ion forms mono-, di- and tri-bromo complexes in both solvents, and their formation constants, enthalpies and entropies were obtained. The Δ H∘₁ value for MnBr⁺ strongly depends on the solvent, i.e., it is positive (19.4 kJ-mol⁻¹) in DMPA and negative (−8.7 kJ-mol⁻¹) in TMU, whereas the Δ H^∘₂ and Δ H∘₃ values for the stepwise formation of MnBr₂ and MnBr₃⁻ are both small and negative. The enthalpy of transfer Δ_tH^∘ from DMPA to TMU, which is evaluated on the basis of the extrathermodynamic TATB assumption, is 25.5 kJ-mol⁻¹ for Mn²⁺ and −3.6 kJ-mol⁻¹ for MnBr⁺. These values indicate that the difference between the formation enthalpy of MnBr⁺ in the two solvents, Δ H^∘₁ (DMPA) – Δ H∘₁ (TMU), is mainly ascribed to the value of Δ_tH^∘(Mn²⁺). It is found that the metal ion is also five-coordinated in the monobromo complex, MnBr(DMPA)₄⁺ . The enthalpy for the conformational change of DMPA from its planar cis to the nonplanar staggered form is evaluated to be −11 and −5.5 kJ-mol⁻¹ for Mn(DMPA)₅^{2 +} and MnBr(DMPA)₄⁺, respectively. Note that these values are significantly smaller than the corresponding value (5.0 kJ-mol⁻¹) in the bulk phase. We thus conclude that, although steric hindrance among solvent molecules is reduced by replacing one DMPA of Mn(DMPA)₅^{2 +} with the relatively small bromide ion, DMPA molecules are still sterically hindered in the MnBr(DMPA)₄⁺ complex.     

X-ray diffraction analysis: A brief history and achievements of the first century

A DFT/B3LYP method using the 6-311++G(3df) basis set is employed to calculate the geometric, electronic, and thermodynamic parameters of O=NO-ON=O peroxide as an isomer of N₂O₄ dinitrogen tetraoxide. Calculations of the configuration interaction in a system of three paramagnetic particles with open shells have shown for the first time that the formation of cis-cis peroxide in the oxidation reaction of nitrogen oxide 2NO (²Π) + O₂ (³Σ_g) → O=NO-ON=O (¹ A) proceeds without an energy barrier in accordance with recently performed studies. The molecular orbital scheme of the barrierless activation of molecular oxygen and the driving force of the NO oxidation reaction are considered. A spontaneous character of the process is based on the idea of spin-catalysis when the reaction proceeds in the two-triplet state with total zero spin. The obtained results are in agreement with the experimental data on a spontaneous and irreversible process characterized by the observed negative activation energy.     

Coordination compounds of cobalt porphyrins with nitrogen monoxide

Complex formation of NO and the NO ₂ ⁻ ion with cobalt porphyrins bearing various substituents in the porphyrin macrocycle, viz., tetraphenylporphine (1), β-octabromo-meso-tetraphenylporphyrin (2), protoporphyrin IX (3), and 5,10,15,20-tetra(4N-carboxymethylene-pyridyl)porphyrin tetrabromide (4), was studied. The stability constants of the nitrosyl and nitrite extracomplexes in water and in ethanol were determined. Porphyrin 4 forms the most stable extracomplexes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 715–718, April, 2007.     

Hemoglobin-stabilized tetranitrosyl binuclear iron complex with pyridine-2-yl in aqueous solutions

The tetranitrosyl iron complex with pyridine-2-yl [Fe₂(SC₅H₄N)₂(NO)₄] (1) has higher NO-donating activity in 3% aqueous solutions of DMSO (pH 7.0, 25 °C) than the organic NO donor, viz., adduct of NO with diethylenetriamine (NO-adduct). The NO concentration was determined by the spectrophotometric method based on the formation of an NO complex with hemoglobin (Hb). The apparent first-order rate constants of the studied reactions are (6.15±0.6)·10⁻¹ s⁻¹ and (0.8±0.08)·10⁻¹ s⁻¹ for complex 1 and the NO-adduct, respectively, at an Hb concentration of 2·10⁻¹ mol L⁻¹ and the ratio [NO donor]/[Hb] = 10. The effect of Hb and [NO donor]/[Hb] ratio on the rate of NO generation from a solution of complex 1 was studied. For a fourfold decrease in the concentration of complex 1 the reaction rate constant decreases to 0.5·10⁻⁴ s⁻¹, whereas the fourfold increase in the Hb concentration results in the stabilization of complex 1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 732–736, April, 2007.     

NO Reduction Over Noble Metal Ionic Catalysts

In last 40 years, catalysis for NO _x removal from exhaust gas has received much attention to achieve pollution free environment. CeO₂ has been found to play a major role in the area of exhaust catalysis due to its unique redox properties. In last several years, we have been exploring an entirely new approach of dispersing noble metal ions in CeO₂ and TiO₂ for redox catalysis. We have extensively studied Ce_1−x M _x O_2−δ (M = Pd, Pt, Rh), Ce_1−x−y A _x M _y O_2−δ (A = Ti, Zr, Sn, Fe; M = Pd, Pt) and Ti_1−x M _x O_2−δ (M = Pd, Pt, Rh, Ru) catalysts for exhaust catalysis especially NO reduction and CO oxidation, structure–property relation and mechanism of catalytic reactions. In these catalysts, lower valent noble metal ion substitution in CeO₂ and TiO₂ creates noble metal ionic sites and oxide ion vacancy. NO gets molecularly adsorbed on noble metal ion site and dissociatively adsorbed on oxide ion vacancy site. Dissociative chemisorption of NO on oxide ion vacancy leads to preferential conversion of NO to N₂ instead of N₂O over these catalysts. It has been demonstrated that these new generation noble metal ionic catalysts (NMIC) are much more catalytically active than conventional nano crystalline noble metal catalysts especially for NO reduction.     

Mechanistic study of the SCR of NO with propylene over Co/ZSM-5 using in-situ FT-IR

The selective catalytic reduction (SCR) of NO with propylene over Co-exchanged ZSM-5 (Co/ZSM-5) was studied using in-situ FTIR. Propylene was activated easily by NO in the absence of oxygen above 200°C, leading to the formation of three different types of surface NCO species; Cobonded (2235 and 2195 cm⁻¹), Si-bonded (2300 cm⁻¹) and Al-bonded (2272 cm⁻¹). These surface NCO species were stable in NO or oxygen atmosphere up to 400°C but in NO+oxygen they were easily converted to the final products of N₂ and CO₂. It is supposed that the SCR of NO over Co/ZSM-5 occurs through the Co- and Al-bonded NCO intermediates and its conversion is the rate-limiting step.     

Reactivity of the Re-NO centre: Proton induced oxidation of Re(NO)2+ to Re(NO)3+. Synthesis and characterisation of some Re(II) thiocyanato-halogenonitrosyl complexes

The Re(NO)²⁺ moiety as [Re(NO)(NCS)₃H₂O]⁻ or [Re(NO)(NCS)₂(L-L)H₂O]· [L-L = phen (1,10-phenanthroline) or bipy (2,2′-bipyridine)] undergoes proton-induced oxidation reaction with HX (X = Cl, Br) to produce a Re(NO)³⁺ moiety. The spectral and physico-chemical data suggest that the anionic complex is 5 coordinate and the neutral one is 6 coordinate with axial NO group and two NCS ligands intrans-equatorial positions. The complex, [Re(NO)(NCS)₂(phen)Br]·H₂O shows complicated magnetic behaviour which is discussed in the paper. The ESR spectrum of this compound shows typical rhenium hyperfines and <g>-tensor anisotropy compatible with the loss of axial symmetry. However, the spectrum of [Re(NO)(NCS)₂Br₂]⁻ quite reasonably shows axial symmetry, other features being grossly comparable to the L-L compounds. The anionic species and the neutral L-L complex show irreversible one-electron oxidation waves at different voltages. This may correspond to a conversion of Re(NO)³⁺ to Re(NO)⁴⁺ in both the cases. Interestingly enough, only the neutral complexes exhibit an irreversible reduction wave due probably to a conversion of Re(NO)³⁺ to Re(NO)²⁺.