16885-04-4Relevant articles and documents
I*(2P1/2) and Cl*(2P 1/2) production from chloroiodobenzenes in the ultraviolet
Senapati, Dulal,Maity, Sandip,Das, Puspendu K.
, p. 7949 - 7953 (2004)
The relative quantum yields of I*(2P1/2) and Cl*(2P1/2) production, φ(I) and φ*(Cl), respectively, have been measured at four different ultraviolet excitation wavelengths, e.g., 222, 236, 266, and 280 nm in the
Selective C-H halogenation over hydroxylation by non-heme iron(iv)-oxo
Rana, Sujoy,Biswas, Jyoti Prasad,Sen, Asmita,Clémancey, Martin,Blondin, Geneviève,Latour, Jean-Marc,Rajaraman, Gopalan,Maiti, Debabrata
, p. 7843 - 7858 (2018/10/31)
Non-heme iron based halogenase enzymes promote selective halogenation of the sp3-C-H bond through iron(iv)-oxo-halide active species. During halogenation, competitive hydroxylation can be prevented completely in enzymatic systems. However, synthetic iron(iv)-oxo-halide intermediates often result in a mixture of halogenation and hydroxylation products. In this report, we have developed a new synthetic strategy by employing non-heme iron based complexes for selective sp3-C-H halogenation by overriding hydroxylation. A room temperature stable, iron(iv)-oxo complex, [Fe(2PyN2Q)(O)]2+ was directed for hydrogen atom abstraction (HAA) from aliphatic substrates and the iron(ii)-halide [FeII(2PyN2Q)(X)]+ (X, halogen) was exploited in conjunction to deliver the halogen atom to the ensuing carbon centered radical. Despite iron(iv)-oxo being an effective promoter of hydroxylation of aliphatic substrates, the perfect interplay of HAA and halogen atom transfer in this work leads to the halogenation product selectively by diverting the hydroxylation pathway. Experimental studies outline the mechanistic details of the iron(iv)-oxo mediated halogenation reactions. A kinetic isotope study between PhCH3 and C6D5CD3 showed a value of 13.5 that supports the initial HAA step as the RDS during halogenation. Successful implementation of this new strategy led to the establishment of a functional mimic of non-heme halogenase enzymes with an excellent selectivity for halogenation over hydroxylation. Detailed theoretical studies based on density functional methods reveal how the small difference in the ligand design leads to a large difference in the electronic structure of the [Fe(2PyN2Q)(O)]2+ species. Both experimental and computational studies suggest that the halide rebound process of the cage escaped radical with iron(iii)-halide is energetically favorable compared to iron(iii)-hydroxide and it brings in selective formation of halogenation products over hydroxylation.
Gas-Phase Reaction of Methyl n-Propyl Ether with OH, NO3, and Cl: Kinetics and Mechanism
Zhu, Jianqiang,Wang, Shuyan,Tsona, Narcisse T.,Jiang, Xiaotong,Wang, Yifeng,Ge, Maofa,Du, Lin
, p. 6800 - 6809 (2017/09/23)
Rate constants at room temperature (293 ± 2 K) and atmospheric pressure for the reaction of methyl n-propyl ether (MnPE), CH3OCH2CH2CH3, with OH and NO3 radicals and the Cl atom have been determined in a 100 L FEP-Teflon reaction chamber in conjunction with gas chromatography-flame ionization detector (GC-FID) as the detection technique. The obtained rate constants k (in units of cm3 molecule-1 s-1) are (9.91 ± 2.30) × 10-12, (1.67 ± 0.32) × 10-15, and (2.52 ± 0.14) × 10-10 for reactions with OH, NO3, and Cl, respectively. The products of these reactions were investigated by gas chromatography-mass spectrometry (GC-MS), and formation mechanisms are proposed for the observed reaction products. Atmospheric lifetimes of the studied ether, calculated from rate constants of the different reactions, reveal that the dominant loss process for MnPE is its reaction with OH, while in coastal areas and in the marine boundary layer, MnPE loss by Cl reaction is also important.
Measuring the rate constant of the reaction between chlorine atoms and CHF2Br by Cl atom resonance fluorescence
Larin,Spasskii,Trofimova,Proncheva
, p. 308 - 312 (2016/07/06)
The rate constant of the reaction between Cl atoms and CHF2Br has been measured by chlorine atom resonance fluorescence in a flow reactor at temperatures of 295–368 K and a pressure of ~1.5 Torr. Lining the inner surface of the reactor with F-32L fluoroplastic makes the rate of the heterogeneous loss of chlorine atoms very low (khet ≤ 5 s–1). The rate constant of the reaction is given by the formula k = (4.23 ± 0.13) × 10–12e(–15.56 ± 1.58)/RT cm3 molecule–1 s–1 (with the activation energy in kJ/mol units). The possible role of this reaction in the extinguishing of fires producing high concentrations of chlorine atoms is discussed.
Mechanism of thermal decomposition of allyltrichlorosilane with formation of three labile intermediates: dichlorosilylene, allyl radical, and atomic chlorine
Boganov,Promyslov,Krylova,Zaitseva,Egorov
, p. 1216 - 1224 (2017/02/05)
It is experimentally found that allyltrichlorosilane dissociates under vacuum pyrolysis (~10–2 Torr) at temperatures above 1100 K to form three labile intermediates: allyl radical, dichlorosilylene, and monoatomic chlorine. On the basis of experimental and theoretical data obtained, it is shown that the decomposition reaction proceeds in two steps. The first step is a typical reaction of homolytic decomposition to two radicals (C3H5 and SiCl3) at the weakest Si—C bond. Due to weakness of the Si—Cl bond in the SiCl3 radical, the energy of which is even somewhat lower than the dissociation energy of the Si—C bond in starting AllSiCl3, this radical undergoes further dissociation to SiCl2 and Cl, thus resulting in three intermediates of different classes of highly reactive species formed from AllSiCl3.
Atmospheric chemistry of CF3CH2OCH3: Reaction with chlorine atoms and OH radicals, kinetics, degradation mechanism and global warming potential
?sterstr?m, Freja From,Nielsen, Ole John,Sulbaek Andersen, Mads P.,Wallington, Timothy J.
, p. 32 - 37 (2012/03/09)
FTIR smog chamber techniques were used to measure k(Cl + CF 3CH2OCH3) = (2.28 ± 0.44) × 10-11 and k(OH + CF3CH2OCH3) = (4.9 ± 1.3) × 10-13 cm3 molecule-1 s-1 in 700 Torr total pressure of air at 296 ± 2 K. The atmospheric lifetime of CF3CH2OCH3 is estimated at 25 days. Reaction of Cl atoms with CF3CH2OCH 3 proceeds 79 ± 4% at the CH3 group and 22 ± 2% at the CH2 group. Reaction with OH radicals proceeds 55 ± 5% at the CH3 group yielding CF3CH2OCHO and 45 ± 5% at the CH2 group yielding COF2 and CH 3OCHO as primary oxidation products. The infrared spectrum of CF 3CH(O)OCH3 was measured and a global warming potential GWP100 = 8 was estimated. The atmospheric chemistry and environmental impact of CF3CH2OCH3 is discussed in context of the use of hydrofluoroethers as CFC substitutes.
Temperature (290-400 K) and pressure (5-900 Torr) dependence of the kinetics of the reactions of chlorine atoms with propene and 1-butene
Kaiser,Wallington
, p. 187 - 192 (2011/02/28)
Rate constants for reactions of chlorine atoms with propene (k1) and 1-butene (k2) were measured relative to that of chlorine atoms with n-butane (k3) at 295-400 K in 5-900 Torr of N2 using gas chromatographic a
Dynamics of Cl (2Pj) atom formation in the photodissociation of fumaryl chloride (ClCO - CH = CH - COCl) at 235 nm: A resonance enhanced multiphoton ionization (REMPI) time-of-flight (TOF) study
Kawade, Monali,Saha, Ankur,Upadhyaya, Hari P.,Kumar, Awadhesh,Naik, Prakash D.,Bajaj
, p. 1538 - 1546 (2011/05/07)
The photodissociation dynamics of fumaryl chloride (ClCO-CH=CH-COCl) has been studied in a supersonic molecular beam around 235 nm using resonance enhanced multiphoton ionization (REMPI) time-of-flight (TOF) technique by detecting the nascent state of the primary chlorine atom. A single laser has been used for excitation of fumaryl chloride and the REMPI detection of chlorine atoms in their spin-orbit states, Cl (2P3/2) and Cl* (2P1/2). We have determined the translational energy distribution, the recoil anisotropy parameter, β, and the spin-orbit branching ratio for chlorine atom elimination channels. To obtain these, measured polarization-dependent and state-specific TOF profiles are converted into kinetic energy distributions, using a least-squares fitting method, taking into account the fragment recoil anisotropies, βi. The TOF profiles for both Cl and Cl* are found to be independent of laser polarization; i.e., β is well characterized by a value of 0.0, within the experimental uncertainties. Two components, namely, the fast and the slow, are observed in the translational energy distribution, P(ET), of Cl and Cl* atoms, and assigned to be formed from different potential energy surfaces. The average translational energies for the fast components of the Cl and Cl* channels are 14.9 ± 1.6 and 16.8 ± 1.6 kcal/mol, respectively. Similarly, for the slow components, the average translational energies of the Cl and Cl* channels are 3.4 ± 0.8 and 3.1 ± 0.8 kcal/mol, respectively. The energy partitioning into the translational modes is interpreted with the help of various models, such as impulsive and statistical models. Apart from the chlorine atom elimination channel, molecular hydrogen chloride (HCl) elimination is also observed in the photodissociation process. The HCl product has been detected, using a REMPI scheme in the region of 236-237 nm. The observation of the molecular HCl in the dissociation process highlights the importance of the relaxation process, in which the initially excited parent molecule relaxes to the ground state from where the molecular (HCl) elimination takes place.
PLP-LIF study of the reactions of chlorine atoms with C2H 2, C2H4, and C3H6 in 2-100 Torr of N2 diluent at 295 K
Iwasaki, Erika,Chiba, Hitoshi,Nakayama, Tomoki,Matsumi, Yutaka,Wallington, Timothy J.
, p. 174 - 178 (2010/09/17)
Pulsed laser photolysis-laser-induced fluorescence (PLP-LIF) techniques were used to study the reactions of Cl(2P3/2) atoms with C2H2 (k1), C2H4 (k 2), and C3/su
Kinetics of the reaction of Cl atoms with CHCl3 over the temperature range 253-313 K
Nilsson, Elna J.K.,Hoff, Janus,Nielsen, Ole John,Johnson, Matthew S.
, p. 160 - 162 (2010/09/17)
The reaction CHCl3 + Cl → CCl3 + HCl was studied in the atmospherically relevant temperature range from 253 to 313 K and in 930 mbar of N2 diluent using the relative rate method. A temperature dependent reaction rate constant, valid in the temperature range 220-330 K, was determined by a fit to the result of the present study and that of Orlando (1999); k = (3.77 ± 0.32) × 10-12 exp((-1011 ± 24)/T) cm3 molecule-1 s-1.
