2602-42-8Relevant academic research and scientific papers
Photochemical reaction channels of OCS with Cl2, ICI, or IBr isolated together in an argon matrix: Isolation of syn-iodocarbonylsulfenyl bromide
Tobon, Yeny A.,Nieto, Laura I.,Romano, Rosana M.,Della Vedova, Carlos O.,Downs, Anthony J.
, p. 2674 - 2681 (2008/10/09)
The photolytically induced reactions of a dihalogen XY (= Cl2, ICl, or IBr) with OCS isolated together in an Ar matrix at about 15 K lead to different photoproducts depending on the natures of X and Y. In addition to the known species ClCO, OCCl2, syn-ClC(O)SCl, syn-ClC(O)SSCl, IC(O)Cl, IC(O)Br, and ^n-BrC(O)SBr, syn-iodocarbonylsulfenyl bromide, yyn-IC(O)SBr, has thus been identified for the first time as'a photoproduct of the reactions involving IBr. The first product to be formed in the reactions with Cl 2 or ICI is the C1CO radical which reacts subsequently with halogen or sulfur atoms or other matrix guests to give the corresponding carbonyl dihalide (OCCl2 and IC(O)Cl), syn-ClC(O)SCl or syn-ClC(O)SSCl. The analogous reaction with IBr affords syn-BrC(O)SBr, IC(O)Br, and syn-IC(O)SBr. The changes have been followed, the products characterized experimentally by IR measurements, and the spectra analyzed in the light of the results of appropriate theoretical calculations.
Matrix isolation FTIR spectroscopic and density functional theoretical studies of the nickel, copper, and silver carbonyl chlorides
Shao, Limin,Zhang, Luning,Zhou, Mingfei,Qin, Qizong
, p. 1137 - 1143 (2008/10/08)
The nickel, copper, and silver metal carbonyl chloride molecules have been prepared and isolated in solid argon by cocondensation of the species generated from 1064 nm laser ablation of metal chlorides with carbon monoxide in excess argon at 11 K. On the
FTIR spectroscopic study of 1,1,1-trifluoro-2-chloroethyl and 1,1,1- trifluoro-2-chloroethylperoxyl radicals
Baskir,Korolev,Nefedov
, p. 519 - 522 (2007/10/03)
A combination of matrix isolation and FTIR spectroscopy was applied to investigate 1,1,1-trifluoro-2-chloroethyl (1) and 1,1,1-trifluoro-2- chloroethylperoxyl (2) radicals. Radical 2 was obtained by vacuum pyrolysis of 1,1,1-trifluoro-2-bromo-2-chloroethane (3). Corresponding peroxyl radicals was generated by co-condensation of pyrolysis products and molecular oxygen in an argon matrix. To assign the experimental bands DFT calculations (B3LYP/6-311G**) were carried out. The fundamental bands of O-O and C-O stretching vibrations of peroxyl radical CF3CHClOO (1102.1, 972.7, cm-1) were identified by their red shifts to 1044.7 and 954.1 cm-1 in the spectra of 18O substituted derivatives. UV photolysis of the radical 2 in the low- temperature matrix produced difluoroformaldehyde CF2O, radicals ClCO, CF3, as well as CO and HCl as the primary photoproducts.
Thermal decomposition of COCl2
Lim,Michael
, p. 211 - 215 (2007/10/02)
The thermal decomposition of COCl2 has been studied in incident shock waves at three different loading pressures and varying [COCl2]0. The kinetics experiments were performed at temperatures between 1400 and 2000 K by monitoring the product Cl atoms using the atomic resonance absorption spectrometric (ARAS) technique. Two decomposition pathways for COCl2 are possible: (1) COCl2 (+M) → COCl + Cl (+M) and (2) COCl2 (+M) → CO + Cl2 (+M). The branching ratios were observed to be 90.5% and 9.5%, respectively. Second-order analysis for the sum of (1) and (2) gave the rate expression kd/[Kr] = (8.0 ± 3.8) × 10-8 exp(-30549 ± 766 K/T) cm3 molecule-1 s-1, with an error of ± 35% at the one standard deviation level. This expression compares favorably to results from the decompositions of CH3Cl, CH2Cl2, and CCl4 and provides evidence to suggest that the ΔH°10 is in the range 70-80 kcal mol-1. Theoretical analysis has also been applied to reaction 1 using Troe's semiempirical methods. The best overall fit is obtained with ΔH°10 = 74.5 ± 1.0 kcal mol-1 and ΔEdown = 1714 cm-1. This ΔH°10 implies ΔfH° (0 K) = -6.3 ± 1.0 kcal mol-1 for COCl. Similar theoretical analysis for reaction 2 suggests a barrier height of 81.35 kcal mol-1.
