2696-92-6Relevant articles and documents
Femtosecond TRIR studies of CINO photochemistry in solution: Evidence for photoisomerization and geminate recombination
Bixby, Teresa J.,Patterson, Joshua D.,Reid, Philip J.
, p. 3886 - 3894 (2009)
The photochemistry of nitrosyl chloride (ClNO) in the solution phase is investigated using Fourier transform infrared (FTIR) and ultrafast time-resolved infrared (TRIR) spectroscopies. The NO-stretch fundamental transition for ClNO dissolved in cyclohexan
New systems for classical nitrosohalogenation of alkenes 2. Generation of nitrosyl chloride in AgNO2-SOCl2 and AgNO 3-SOCl2 systems
Bondarenko,Gavrilova,Tikhanushkina,Zyk
, p. 2145 - 2149 (2005)
Study of the reactions of compounds of the norbornene series demonstrated that the AgNO2-SOCl2 and AgNO3-SOCl2 systems serve as nitrosochlorinating agents under the conditions of electrophilic addition. X-ray di
Synthesis and structures of CuI,II complexes with a 2,2′-bipyridine derivative bearing a (+)-3-carene moiety
Kokina,Glinskaya,Piryazev,Baranov, A. Yu.,Agafontsev,Eremina, Yu. A.,Vorontsova,Bogomyakov,Naumov, D. Yu.,Tkachev,Larionov
, p. 1251 - 1260 (2018)
The complex salt {[CuL2][Cu4I6]?MeCN}n (1) and the compound [Cu4L3I4]?3 MeCN (2) (L is a chiral ligand bearing a natural monoterpene (+)-3-carene moiety) were synthesized. The crystal structures of compounds 1 and 2 were determined by X-ray diffraction. The structure of compound 1 consists of complex cations [CuL2]2+ (N3O2 polyhedron is a trigonal bipyramid) and CuI coordination polymers (CuI4 polyhedron is a tetrahedron) as anions. The experimental magnetic moment μeff at 300 K is 1.90 μB, which is consistent with the X-ray diffraction data and the assumption that compound 1 is mixed-valence. The structure of compound 2 comprises a tetranuclear CuI complex, in which three Cu atoms are coordinated by two N atoms of the ligand L and two I atoms, and the fourth Cu atom is coordinated by four I atoms (coordination polyhedra are distorted tetrahedra). Compounds L and 2 were found to influence the viability of human laryngeal carcinoma cells (Hep2). The IC50 value for complex 2 (13.0±1.7 μM) is substantially smaller than IC50 for compound L (30.5±0.5 μM).
Multistate photochemical reaction dynamics of ClNO in solution: An absolute resonance Raman intensity analysis study
Nyholm, Bethany P.,Reid, Philip J.
, p. 8716 - 8724 (2004)
The excited-state reaction dynamics of nitrosyl chloride (ClNO) are studied using absolute resonance Raman intensity analysis. The absolute resonance Raman cross sections for ClNO dissolved in cyclohexane and acetonitrile are measured at several excitation wavelengths spanning the absorption band commonly referred to as the A band (??max a?? 200 nm). The resonance Raman and absorption cross sections are modeled using the time-dependent formalism. Resonance Raman depolarization ratios are also measured and are found to be consistent with at least two electronic transitions participating in the scattering process. Therefore, the standard time-dependent formalism approach was modified by incorporating two excited states into the analysis, with state contributions deconvolved through modeling of the depolarization ratios in addition to the absolute resonance Raman and absorption cross sections. The spectroscopic observables are well reproduced using this two-state model. The analysis presented here demonstrates that the photoexcitation of solution-phase ClNO results in a substantial evolution of the N-Cl stretch coordinate consistent with the dissociation of the N-Cl bond. Significant structural evolution is also observed along the bend, with minimal excited-state structural evolution observed along the N=O stretch. The structural evolution along the dissociative N-Cl stretch coordinate is found to be solvent-dependent, and the origin of this dependence is related to changes in the ground-state equilibrium geometry as a function of solvent environment. Finally, the homogeneous line width undergoes a significant increase in acetonitrile relative to cyclohexane, and this increase is proposed to reflect the modification of the excited-state interactions and nonadiabatic relaxation dynamics.
Differing reactivities of (trimpsi)M(CO)2(NO) complexes [M = V, Nb, Ta; trimpsi = tBuSi(CH2PMe2)3] with halogens and halogen sources
Hayton, Trevor W.,Legzdins, Peter,Patrick, Brian O.
, p. 5388 - 5396 (2002)
Treatment of (trimpsi)V(CO)2(NO) (trimpsi: rBuSi(CH2PMe2)3) with 1 equiv of PhlCl2 or C2Cl6 or 2 equiv of AgCl affords (trimpsi)V(NO)Cl2 (1) in moderate yields. Likewise, (trimpsi)V(NO)Br2 (2) and (trimpsi)V(NO)l2 (3) are formed by the reactions of (trimpsi)V(CO)2(NO) with Br2 and l2, respectively. The complexes (trimpsi)M(NO)l2(PMe3) (M = Nb, 4; Ta, 5) can be isolated in moderate to low yields when the (trimpsi)M(CO)2(NO) compounds are sequentially treated with 1 equiv of 12 and excess PMe3. The reaction of (trimpsi)V(CO)2(NO) with 2 equiv of CINO forms 1 in low yield, but the reactions of (trimpsi)M(CO)2(NO) (M = Nb, Ta) with 1 equiv of CINO generate (trimpsi)M(NO)2Cl (M = Nb, 6; Ta, 7). Complexes 6 and 7 are thermally unstable and decompose quickly at room temperature; consequently, they have been characterized solely by IR and 31 P{1H} NMR spectroscopies. All other new complexes have been fully characterized by standard methods, and the solid-state molecular structures of 1·3CH2Cl2, 4·(3/4)CH2Cl2, and 5·THF have been established by single-crystal X-ray diffraction analyses. A convenient method of generating Cl15NO has also been developed during the course of these investigations.
Atmospheric chemistry of C2F5CHO: reaction with Cl atoms and OH radicals, IR spectrum of C2F5C(O)O2NO2
Andersen, M. P. Sulbaek,Hurley, M. D.,Wallington, T. J.,Ball, J. C.,Martin, J. W.,Ellis, D. A.,Mabury, S. A.,Nielsen, O. J.
, p. 28 - 36 (2003)
Smog chamber/FTIR techniques were used to measure k(Cl + C2F5CHO) = (1.96+/-0.28) x 10-12 and k(OH + C2F5CHO) = (5.26+/-0.80) x 10-13 cm3 molecule-1 s-1 in 700 Torr of N2 or air at 296+/-2 K. The Cl i
Kinetic study of an autocatalytic reaction: Nitrosation of formamidine disulfide
Francisco, Vitor,Garcia-Rio, Luis,Antonio Moreira, Jose,Stedman, Geoffrey
, p. 2292 - 2298 (2008)
The reaction kinetics for the acid nitrosation of formamidine disulfide (FDS) show an autocatalytic behavior that arises from the fact that the thiocyanate ion formed as a product acts as a powerful catalyst for the nitrosation reaction. In the presence of added nucleophiles the suppression of the autocatalytic route results from competition for the nitrous acid between the added halides and the thiocyanate anion, which is formed as a reaction product. Analysis of the kinetic data enabled extraction of the bimolecular rate constants, kNO+ = (3.2 ± 1.8) × 1010 M -1 s-1; kNOSCN = (2.1 ± 0.2) × 105 M-1 s-1; kNOBr = (9.4 ± 0.2) × 106 M-1 s1 and kNOCl = (4.0 ± 0.2) × 107 M-1 s-1, for the pathways catalyzed by SCN-, Br- and Cl-, respectively. Kinetic results are consistent with the attack on the nitrosating agent as the rate limiting step, i.e., the nitrosation of FDS behaves in a similar manner to the nitrosation of an amine. Rather different behavior is found for other substrates with an imino moiety adjacent to an amino nitrogen, such as the guanidines, which react by a mechanism in which the rate limiting step is the reorganization of the nitrosated substrate. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008.
New details concerning the reactions of nitric oxide with vanadium tetrachloride
Hayton, Trevor W.,Patrick, Brian O.,Legzdins, Peter
, p. 7227 - 7233 (2004)
The slow addition of NO to a CCl4 solution of VCl4 reproducibly forms the known polymer [V(NO)3Cl2 ]n as a dark brown powder. Treatment of a CH2Cl 2 suspension of [V(NO)3Cl2]n with excess THF generates mer-(THF)3V(NO)Cl2 (1) which can be isolated as an orange crystalline material in 55% yield. The reaction of 1 with excess MeCN or 1 equiv of trimpsi (trimpsi = tBuSi(CH 2PMe2)3) provides yellow-orange (MeCN) 3V(NO)Cl2·MeCN (2·MeCN) and yellow (trimpsi)V(NO)Cl2 (3), respectively. A black, crystalline complex formulated as [NO][VCl5] (4) is formed by the slow addition of NO to neat VCl4 or by the reaction of excess CINO with neat VCl 4. Complex 4 is extremely air- and moisture-sensitive, and IR spectroscopy suggests that in solutions and in the gas phase it dissociates back into VCl4 and CINO. Reaction of 4 with excess [NEt 3(CH2Ph)]CI generates [NEt3(CH 2Ph)]2[VCl6]·2CH2Cl 2 (5·2CH2Cl2), which can be isolated as deep-red crystals in 51% yield. All new complexes have been characterized by conventional spectroscopic methods, and the solid-state molecular structures of 1, 2·MeCN, and 5·2CH2Cl2 have been established by single-crystal X-ray diffraction analyses.
Diffuse reflectance infrared studies of the reaction of synthetic sea salt mixtures with NO2: A key role for hydrates in the kinetics and mechanism
Langer, Sarka,Pemberton, R. Sean,Finlayson-Pitts, Barbara J.
, p. 1277 - 1286 (1997)
The heterogeneous reactions of oxides of nitrogen with NaCl as a model for sea salt particles have been the focus of many studies, due to their potential to act as precursors to atomic halogens in the troposphere. While a great deal has been learned about the kinetics and mechanisms of NaCl reactions, it is not clear how well this extrapolates to the complex mixture of inorganics found in sea salt. We report here diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) studies in which nitrate formation on the salt surface is followed with time during the reaction of gaseous NO2 with synthetic sea salt at 298 K in the presence of either He or air as the carrier gas. The infrared bands due to surface nitrate formed during the reaction of NO2 are shown to be similar to those from the reaction of MgCl2·OH2O, a major hydrate in the mixture which was used as a surrogate for all of the crystalline hydrates. Significant amounts of surface-adsorbed water are generated in the reaction of synthetic sea salt with NO2 in air, which appears at least in part to be due to liberation of bound water of hydration in the crystalline hydrates. The reaction order with respect to NO2 is (1.8 ± 0.2) (2σ) when the reaction of the synthetic sea salt is carried out in He but only (1.2 ± 0.2) (2σ) when air is used as the carrier gas. For comparison, the reaction order for the NO2-NaCl reaction was reexamined and found to be (1.8 ± 0.3) (2σ) in He and (1.6 ± 0.3) (2σ) in air, in agreement with previous work19 using this technique. It is assumed for slopes ≥ 1.6 that N2O4 is the reacting species for the purpose of expressing the kinetics in the usual form of reaction probabilities. For the N2O4-NaCl reactions in He and air, and for the N2O4-synthetic sea salt reaction in He, the reaction probabilities are similar (～10-4). The reaction of synthetic sea salt with NO2 in the presence of air is treated in terms of a first-order reaction with NO2 being the reactive species, which gives a reaction probability for the NO2-synthetic sea salt reaction of ～10-8. The atmospheric implications are discussed.
Temperature Dependence of the OH + ClNO Reaction: Evidence for two Competing Reaction Channels
Finlayson-Pitts, B. J.,Ezell, M. J.,Grant, C. E.
, p. 17 - 19 (1986)
The temperature dependence of the reaction of OH with nitrosyl chloride, ClNO, has been studied from 263 to 373 K in a fast-flow discharge system.The decay of OH in the presence of excess ClNO was followed by resonance fluorescence at 309.5 nm.The total pressure was 1.05+/-0.05 torr in He as the carrier gas.The rate constant increases both above and below room temperature suggesting the existence of two competing reaction paths, a direct abstraction reaction, HO + ClNO -> HOCl + NO (1a) and one involving formation of an intermediate complex, HO + ClNO * -> HONO + Cl (1b).This supports the interpretation of the room temperature product data of Poulet and co-workers.
