- Structure, Harmonic Force Field and Hyperfine Coupling Constants of Nitrosyl Chloride
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The pure rotational spectra of five isotropic species of nitrosyl chloride were measured using a cavity pulsed microwave Fourier-transform spectometer.Some a-type transitions of all five isotopomers, and some weak b-type transitions of four of these isotopomers were measured in the 4-26 GHz frequency range.Precise values for the rotational constants and the quartic centrifugal distortion constants were obtained.The rotational constants were used in structure determinations and the centrifugal distortion constants were used in a refinement of the harmonic general valence force field.A harmonic central valence force field was also calculated.Hyperfine structure in these transitions arising from quadrupole and spin-rotation coupling interactions was also observed.Diagonal and off-diagonal quadrupole coupling constants and diagonal spin-rotation coupling constants of both the chlorine and nitrogen nuclei were determined.The principal quadrupole coupling constants were evaluated and used to calculate the approximate ionic character of the N-Cl bond.The spin-rotational coupling constants were used to calculate the diamagnetic shielding factor for the nitrogen nucleus; the magnitude of this value indicates a fairly ionic N-Cl bond.
- Gotehouse, Bethany,Meuller, Holger S. P.,Heineking, Nils,Gerry, Michael C. L.
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- Six-coordinate nitro complexes of iron(III) porphyrins with trans S-donor ligands. Oxo-transfer reactivity in the solid state
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Spectroscopic studies demonstrate that the 5-coordinate O-nitrito complexes Fe(Por)(η1-ONO) (Por - mesotetraphenyl- or meso-tetra-p-tolyl- porphyrinato dianions) react with the thioethers (R2S) dimethylsulfide and tetrahydrothiophene
- Kurtikyan, Tigran S.,Hovhannisyan, Astghik A.,Iretskii, Alexei V.,Ford, Peter C.
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- Six-coordinate nitrosyl and nitro complexes of meso - Tetratolylporphyrinatocobalt with trans sulfur-donor ligands
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By Fourier transform infrared and optical spectroscopy, it has been observed that interactions of dimethyl sulfide and tetrahydrothiophene with nitrosyl and nitro complexes of meso-tetra-p-tolylporphyrinatocobalt [Co(TTP)] lead to the formation of previou
- Kurtikyan, Tigran S.,Gulyan, Gurgen M.,Dalaloyan, Arina M.,Kidd, Bryce E.,Goodwin, John A.
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p. 7793 - 7798
(2010/12/20)
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- Interaction of nitrogen bases with iron-porphyrin nitrito complexes Fe(Por)(ONO) in sublimed solids
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The reactions of the nitrogen Lewis bases (B) 1-methylimidazole (1-Melm), pyridine (Py), and NH3 as gases with sublimed layers containing the 5-coordinate nitrito iron(III)-porphyrinato complexes Fe(Por)(η1- ONO) (1) are described (P
- Kurtikyan, Tigran S.,Hovhannisyan, Astghik A.,Gulyan, Gurgen M.,Ford, Peter C.
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p. 7024 - 7031
(2008/10/09)
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- Reactions of nitrogen oxides with heme models: Spectral characterization of an elusive five-coordinate FeIII(porphyrin) nitrito intermediate
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(Chemical Equation Presented) The famous five: The elusive five-coordinate nitrito complexes [FeIII(por)(ONO)] (por = meso- tetraphenylporphyrinato dianion or meso-tetra-p-tolylporphyrinato dianion) have been obtained by interaction of low-pres
- Kurtikyan, Tigran S.,Ford, Peter C.
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p. 492 - 496
(2007/10/03)
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- 14N/15N kinetic isotope effect in the association reaction O(3P)+NO+Ar→NO2+Ar
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The termolecular rate constants for the O(3P)+14NO+Ar→14NO2+Ar and O(3P)+15NO+Ar→15NO2+Ar reactions were determined under room temperature bulk conditions. O(3P) was produced by the pulsed photodissociation of SO2 at 210.4 nm and was monitored by two-photon laser-induced fluorescence at 225.7 nm. The rate constants for 14NO and 15NO were determined to be 5.4±0.2 and 6.1±0.3×10-32cm6s-1, respectively. The error limits are twice the standard errors (S.E.). This isotope effect is opposite to that expected from a statistical model but is similar to that observed in the O3 formation reactions from O(3P) and O2.
- Umemoto, Hironobu,Tanaka, Kunikazu,Oguro, Shigeki,Ozeki, Ryoji,Ueda, Masashi
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- Direct synthesis of nitroamine extracomplexes of Cobalt(II) meso-tetraphenylporphyrinate with the use of its sublimed layers
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IR spectroscopy and isotope-substituted 15NO2 were used to show that the pentacoordinate nitro complex CoTPhP · NO2 obtained by the direct reaction of nitrogen dioxide with sublimed layers of cobalt mesotetraphenylporphyrinate (CoTPhP) easily transforms in an atmosphere of amines (B) into the corresponding hexacoordinate nitroamine extracomplexes B · CoTPhP · NO2 (B = NH3, C5H11N, and C5H5N). Because of their specific supramolecular structure, the sublimed layers of pentacoordinate complexes retain the ability to coordinate additional ligands at the sixth coordination site, and thus, they can serve as a basis for generating axial mixed-ligand extracomplexes.
- Stepanyan,Akopyan,Kurtikyan
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p. 425 - 428
(2008/10/08)
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- 15N nuclear polarization in the reactions of diallyl ether with nitrogen dioxide
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The reaction of diallyl ether with nitrogen dioxide in organic solvents yields a mixture of cis and trans 2,3-bis(nitromethyl)-tetrahydrofurans, cis and trans 2-nitratomethyl-3-nitromethyl-tetrahydrofurans and a number of straightchain compounds with one to four nitro groups. Under the conditions used, the cyclic compounds form the main products when the solution of nitrogen dioxide is slowly added to the solution of diallyl ether but not when the reverse mode of addition is used. When 15N-nitrogen dioxide is used, the products show strong 15N nuclear polarization: the 2,3-di(nitromethyl)-tetrahydofurans give an emission signal, and one straight-chain product with two nonequivalent nitro groups shows both an emission signal and an enhanced absorption signal. For both the cyclic and straight-chain products, the nuclear polarization is consistent with the successive reactions of diallyl ether with two nitrogen dioxide radicals with uncorrelated spins.
- Claridge, Robert P.,Millar, Ross W.,Ridd, John H.
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p. 647 - 653
(2007/10/03)
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- Remarkable oxygen promotion of the selective reduction of nitric oxide by hydrogen over Au/NaY and Au/ZSM-5 zeolite catalysts
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A significant enhancement of the selective reduction of nitrogen oxide by H2 is produced in the presence of oxygen over Au/NaY and Au/ZSM-5 catalysts by forming NO2 and N2O4 intermediates, which are eventually reduced to N2.
- Salama, Tarek M.,Ohnishi, Ryuichiro,Ichikawa, Masaru
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p. 105 - 106
(2007/10/03)
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- Spin Trapping of Nitrogen Dioxide from Photolysis of Sodium Nitrite, Ammonium Nitrate, Ammonium Dinitramide, and Cyclic Nitramines
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Nitrogen dioxide (NO2.), produced by photodecomposition (λ > 200 nm) of polycrystalline sodium nitrite (Na+NO2-), polycrystalline energetic oxidizers, ammonium nitrate (NH4+NO3-), and ammonium dinitramide +N(NO2)2->, and the polycrystalline cyclic nitramine cyclotrimethylenetrinitramine (RDX), was studied by electron spin resonance (ESR) spin trapping at room temperature (300 K) and by matrix isolation ESR spectroscopy at 77 K.In spin trapping experiments, the aci anion of nitromethane (CH2=NO2-) was used to spin trap NO2. produced by photodecomposition of these energetic compounds in basic (pH > 13) aqueous solutions at room temperature.The resulting NO2. adduct radical is the dinitromethyl anion radical (DNM.) (-NO2-CH=NO2.-) which gives a 10-line ESR spectrum.For equimolar starting concentrations of each compound, the ESR signal intensities of the DNM. spectrum varied according to NaNO2 > NH4N(NO2)2 > NH4NO3 > RDX.From kinetics of DNM. formation, the suggested dominant mechanisms of NO2. formation are NO2- + OH. -> NO2. + OH- for compounds NaNO2 and RDX and NO33-7 -> NO2. + O- for NH4NO3 and NH4N(NO2)2.Two other cyclic nitramines, cyclotetramethylenetetranitramine (HMX) and hexanitrohexaazaisowurtzitane (HNIW), were confirmed to give weak DNM. adduct ESR signals.In matrix isolation ESR experiments at 77 K, the rate of formation of NO2. is zero-order for NaNO2 and NH4NO3 but first-order for NH4N(NO2)2 under the photolysis conditions of this experiment, suggesting that, in the solid phase, NO2. is formed by different mechanisms in the two ammonium salts.
- Pace, M. D.
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p. 6251 - 6257
(2007/10/02)
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