7698-05-7Relevant articles and documents
Kinetic study of the reaction of chlorine atoms with chloroform in the gas phase
Gola, Agnieszka A.,Sarzyński, Dariusz,Dry?, Andrzej,Jodkowski, Jerzy T.
, p. 250 - 254 (2009)
The kinetics of the gas-phase reactions of chlorine atoms with H-chloroform and D-chloroform was studied experimentally. The relative rate method was applied using Cl + CH3Br as the reference reaction. The rate constants for H-abstraction from
Kinetic study of the reaction of chlorine atoms with chloromethane in the gas phase
Sarzyński, Dariusz,Gola, Agnieszka A.,Dry?, Andrzej,Jodkowski, Jerzy T.
, p. 138 - 142 (2009)
The kinetics of the gas phase reactions of chlorine atoms with chloromethane and D-chloromethane CD3Cl was studied experimentally. The relative rate method was applied using Cl + CH3Br as the reference reaction. The rate constants fo
Differential cross section polarization moments: Location of the D-atom transfer in the transition-state region for the reactions CI+C2D6→DCI(v′= 0, J′=1)+C2D5 and CI+CD4→DCI(v′=0,J′=1)+CD3
Rakitzis, T. Peter,Kandel, S. Alex,Lev-On, Topaz,Zare, Richard N.
, p. 9392 - 9405 (1997)
The photoloc technique can permit the measurement of not only the state-to-state differential cross section but also its complete product polarization dependence for all moments of orientation and alignment with K≤2. We have realized this possibility for the reaction Cl+C2D6→DCl(v′=0,J′ =1)+C2D5 at a collision energy of 0.25 eV, for which we have measured the differential cross section, 1lσ(dσ00/dΩr), and the four polarization-dependent moments of the differential cross section, A1(1)stf, A0(2)stf, A1(2)stf and A2(2)stf, in the stationary target frame (STF), which are defined by Aq(k)stf=(dσkq stf/dΩr)/(dσ00/dΩ r). For the Cl+CD4→DCl(v′=0,J′=1)+CD3 reaction at a collision energy of 0.28 eV we have also determined 1/σ(dσ00/dΩr) and A0(2)stf. The laboratory speed distributions of the DCl(v′=0,J′=1) products are measured using 2+1 resonance-enhanced multiphoton ionization (REMPI) and the core-extraction technique. The polarization-dependent differential cross sections are determined from the dependence of the core-extracted profiles on the photolysis and probe polarizations. Recent studies have shown that the Cl+CD4 and Cl+C2D6 both show scattering behavior described by the line-of-centers model and both yield rotationally cold DCl products with little energy in the alkyl fragments. Despite these similarities, we measure DCl(v′=0,J′=1) product polarizations that differ greatly for these two reactions. For the Cl+CD4 reaction, we find that JDCl is maximally aligned perpendicular to an axis close to the product scattering direction, uDCl. For the Cl+C2D6 reaction, we find that JDCl is half-maximally aligned perpendicular to the line-of-centers direction. We interpret these results in terms of the location of the D-atom transfer along the reaction coordinate, positing that the D-atom transfer for the Cl+CD4 reaction occurs late in the reactive process and the D-atom transfer for the Cl+C2D6 reaction occurs earlier near the distance of closest approach. We interpret the difference in the locations of the D-atom transfer to be the cause of the large differences in the Arrhenius pre-exponential factors of the C1+CD4 and Cl+C2D6 reactions.
H/D isotope effects on formation and photodissociation of HKrCl in solid Kr
Khriachtchev, Leonid
, p. 6403 - 6410 (2003)
The H/D isotope effects on formation and photodissociation of HKrCl in solid Kr were investigated. The formation kinetics of HKrCl and DKrCl reveals the isotope effect on thermally activated mobility of atomic hydrogen. Thus, the difference between the H and D mobilities allowed to show that a reaction of D atoms with HKrCl was taking place. Thus, the HKrCl and DKrCl photodecomposition rates were compared.
Infrared spectra and theoretical calculations of HCl complexed with NO
Krim,Alikhani
, p. 265 - 271 (1998)
The vibrational spectra of NO:HCl trapped in argon matrix have been reinvestigated. In the high frequency region, two stretching modes of N-O and H-Cl have been observed in agreement with a recent paper [Chem. Phys. 185 (1994) 365]. In the low frequency region, two bands (N-H stretch and out of plane bend) have been identified. From a theoretical study, it has been shown that the four experimental frequencies of the complex are well reproduced only for a bent structure in which H-bonding takes place between the nitrogen atom of NO and the hydrogen atom of HCl. The calculated frequency shifts of the N-O and H-Cl stretching modes upon complexation agree well with the experimental values.
Infrared Spectroscopic and Electronic Structure Investigations of Beryllium Halide Molecules, Cations, and Anions in Noble Gas Matrices
Yu, Wenjie,Andrews, Lester,Wang, Xuefeng
, p. 8843 - 8855 (2017)
Laser-ablated Be atoms, cations, and electrons were reacted with F2, ClF, Cl2, NF3, CCl4, CF2Cl2, HCl, DCl, and SiCl4 diluted in noble gases. The major products were the dihalides BeF2, BeClF, BeCl2, and the hydride chloride HBeCl, whose identities were confirmed by comparison with previous evaporative work, deuterium substitution, and vibrational frequency calculations. The matrix-isolated fundamental frequency of the BeF molecule is higher, and the frequency of BeCl is lower, than that determined for the gas-phase molecules. The BeF+ and BeCl+ cations formed strong dipole-induced dipole complexes in solid Ne, Ar, Kr, and Xe with stepwise increase in computed noble gas dissociation energies. Going down the family NgBeF+ and NgBeCl+ series (Ng = Ne, Ar, Kr, Xe) the Mulliken charges q(Be) decrease, while q(Ng) increases, and the dipole moments decrease, which suggests covalent bonding in the xenon species. We find that the largest intramatrix shift is Ne to Ar which follows the largest factor increase for the Ng atomic polarizabilities. Extra electrons produce Cl-, which reacts with HCl to form the stable HCl2- anion and possibly with BeCl2 to give BeCl3-. A weak band observed in neon experiments with F2 is probably due to BeF3-.
Kinetics of the Cl-H2 system. II. Abstraction vs exchange in D+HCl
Miller, John C.,Gordon, Robert J.
, p. 3713 - 3720 (1983)
The gas phase reaction of D with HCl was studied at room temperature by the method of flash photolysis, with resonance fluorescence detection of D, H, and Cl atoms.The D and Cl atoms were observed to decay exponentially, whereas no H atom signal the excha
Infrared Spectra of the HAnX and H2AnX2 Molecules (An=Th and U, X=Cl and Br) in Argon Matrices Supported by Electronic Structure Calculations
Li, Lin,Stüker, Tony,Andrews, Lester,Beckers, Helmut,Riedel, Sebastian
, p. 1795 - 1805 (2019)
Uranium and thorium hydrides are known as functional groups for ligand stabilized complexes and as isolated molecules under matrix isolation conditions. Here, the new molecular products of the reactions of laser-ablated U and Th atoms with HCl and with HBr, namely HUCl, HUBr and HThCl, HThBr, based on their mid and far infrared spectra in solid argon, are reported. The assignment of these species is based on the close agreement between observed and calculated vibrational frequencies. The H?U and U?35Cl stretching modes of HUCl were observed at 1404.6 and 323.8 cm?1, respectively. Using DCl instead to form DUCl gives absorption bands at 1003.1 and 314.7 cm?1. The corresponding bands of HThCl are 1483.8 (H?Th) and 1058.0 (D?Th), as well as 340.3 and 335.8 cm?1 (Th?35Cl), respectively. HUBr is observed at 1410.6 cm?1 and the BP86 computed shift from HUCl is 6.2 cm?1 in excellent agreement. The U?H stretching frequency increases from 1383.1 (HUF), 1404.6 (HUCl), 1410.6 (HUBr) to 1423.6 cm?1 (UH) as less electronic charge is removed from the U?H bond by the less electronegative substituent. These U?H stretching frequencies follow the Mayer bond orders calculated for the three HUX molecules. A similar trend is found for the Th counterparts. Additional absorptions are assigned to the H2AnX2 molecules (An=U, Th, X=Cl, Br) formed by the exothermic reaction of a second HX molecule with the above primary products.
Kinetics of the Cl-H2 system. III. The deuterium isotope effect in Cl + H2
Miller, John C.,Gordon, Robert J.
, p. 1252 - 1258 (1983)
The rate constant for the reaction Cl+D2 was measured over the temperature range 200-500 K, using the flash photolysis-resonance fluorescence technique.These data, together with previous measurements for Cl+H2, are compared with the isotope effect measured by Persky and Klein in a static bulb.Over the range 295-500 K, our data are in excellent agreement with their results.At lower temperatures, the Cl+D2 rate constant displays an anomalous non-Arrhenius curvature.A mechanism involving the reaction of Cl atoms with vibrationally excited D2 is proposed to explain this effect.
Reactivity of auranofin with selenols and thiols - Implications for the anticancer activity of gold(I) compounds
Di Sarra, Francesca,Fresch, Barbara,Bini, Riccardo,Saielli, Giacomo,Bagno, Alessandro
, p. 2718 - 2727 (2013/07/11)
The enzyme thioredoxin reductase (TrxR) is attracting much interest as a potential target for cancer therapy. The presence of a selenium atom in the catalytic site makes it sensitive to inhibition by electrophilic molecules, including the AuI complex auranofin [2,3,4,6-tetra-O-acetyl-1-thio- β-D-glucopyranosato-S-(triethylphosphane)gold]. The reactions between auranofin and models of thiol and selenol nucleophiles present in TrxR (PhSH and PhSeH) have been investigated in chloroform and methanol by means of 1H, 31P, and 77Se NMR spectroscopy. In chloroform, auranofin undergoes ligand substitution of the tetraacetylthioglucose moiety by a PhS or PhSe group. The reaction is reversible in both cases, but it is characterized by widely different equilibrium constants (ca. 1 for S and at least 103 for Se). In polar solvents, such as methanol, the reaction is more complex, and the phosphane moiety also undergoes ligand exchange. Some features have been clarified through the investigation of Et3PAuCl. The elementary processes involved have been characterized by DFT calculations. Copyright
