463-58-1Relevant academic research and scientific papers
Isomers of HSCO: IR absorption spectra of t-HSCO in solid Ar.
Lo, Wen-Jui,Chen, Hui-Fen,Wu, Yu-Jong,Lee, Yuan-Pern
, p. 5717 - 5722 (2004)
Irradiation of an Ar matrix sample containing H2S and CO (or OCS) with an ArF excimer laser at 193 nm yields trans-HSCO (denoted t-HSCO). New lines at 1823.3, 931.6, and 553.3 cm(-1) appear after photolysis and their intensity enhances after annealing; secondary photolysis at 248 nm diminishes these lines and produces OCS and CO. These lines are assigned to C-O stretching, HSC-bending, and C-S stretching modes of t-HSCO, respectively, based on results of 13C-isotopic experiments and theoretical calculations. Theoretical calculations using density-functional theories (B3LYP and PW91PW91) predict four stable isomers of HSCO: t-HSCO, c-HSCO, HC(O)S, and c-HOCS, listed in increasing order of energy. According to calculations with B3LYP/aug-cc-pVTZ, t-HSCO is planar, with bond lengths of 1.34 A (H-S), 1.81 A (S-C), and 1.17 A (C-O), and angles angle HSC congruent with 93.4 degrees and angle SCO congruent with 128.3 degrees; it is more stable than c-HSCO and HC(O)S by approximately 9 kJ mol(-1) and more stable than c-HOCS by approximately 65 kJ mol(-1). Calculated vibrational wave numbers, IR intensities, and 13C-isotopic shifts for t-HSCO fit satisfactorily with experimental results. This new spectral identification of t-HSCO provides information for future investigations of its roles in atmospheric chemistry. (c) 2004 American Institute of Physics
Carbonyl sulfide hydrolase from thiobacillus thioparus strain thi115 is one of the β-carbonic anhydrase family enzymes
Ogawa, Takahiro,Noguchi, Keiichi,Saito, Masahiko,Nagahata, Yoshiko,Kato, Hiromi,Ohtaki, Akashi,Nakayama, Hiroshi,Dohmae, Naoshi,Matsushita, Yasuhiko,Odaka, Masafumi,Yohda, Masafumi,Nyunoya, Hiroshi,Katayama, Yoko
, p. 3818 - 3825 (2013)
Carbonyl sulfide (COS) is an atmospheric trace gas leading to sulfate aerosol formation, thereby participating in the global radiation balance and ozone chemistry, but its biological sinks are not well understood. Thiobacillus thioparus strain THI115 can grow on thiocyanate (SCN-) as its sole energy source. Previously, we showed that SCN- is first converted to COS by thiocyanate hydrolase in T. thioparus strain THI115. In the present work, we purified, characterized, and determined the crystal structure of carbonyl sulfide hydrolase (COSase), which is responsible for the degradation of COS to H2S and CO2, the second step of SCN- assimilation. COSase is a homotetramer composed of a 23.4 kDa subunit containing a zinc ion in its catalytic site. The amino acid sequence of COSase is homologous to the β-class carbonic anhydrases (β-CAs). Although the crystal structure including the catalytic site resembles those of the β-CAs, CO2 hydration activity of COSase is negligible compared to those of the β-CAs. The α5 helix and the extra loop (Gly150-Pro158) near the N-terminus of the α6 helix narrow the substrate pathway, which could be responsible for the substrate specificity. The k cat/Km value, 9.6 × 105 s-1 M-1, is comparable to those of the β-CAs. COSase hydrolyzes COS over a wide concentration range, including the ambient level, in vitro and in vivo. COSase and its structurally related enzymes are distributed in the clade D in the phylogenetic tree of β-CAs, suggesting that COSase and its related enzymes are one of the catalysts responsible for the global sink of COS.
Rate Constant for the Reaction between OH and CS2 at 298 and 520 K
Leu, Ming-Taun,Smith, Roland H.
, p. 958 - 961 (1982)
In an attempt to resolve discrepancies between published values of the rate constant for the reaction between hydroxyl radical and carbon disulfide, the reaction has been studied in a discharge flow system by using resonance fluorescence for kinetic measurements and mass spectrometry for product analysis.On the basis of the measured rate constant for disappearance of OH and measurements of the amount of carbonyl sulfide formed, it was estimated that for the reaction HO + CS2 -> HS + OCS, k 3s-1 at 520 K and 3s-1 at 298 K, upper limits being specified because of the inability to isolate exclusively this reaction channel, and because of possible involvement of wall reactions.These results confirm the low values found for this rate constant in two very recent studies.
Selection of the type of methane conversion for catalytic reduction of sulfur dioxide
Kasumova
, p. 196 - 201 (2012)
Catalytic reduction of sulfur dioxide with converted gas obtained by various methods of conversion of natural gas was studied to select the most active reducing agent for SO2. Pleiades Publishing, Ltd., 2012.
Direct formation of Ge-C bonds from GeO2
Lewis, Larry N.,Litz, Kyle E.,Anostario, Joseph M.
, p. 11718 - 11722 (2002)
Germanium dioxide in the presence of 5% KOH reacted with dimethyl carbonate (DMC) at 250 °C to give (MeO)4Ge. The reaction of GeO2 and DMC is similar to that reported for SiO2; however, the rate of reaction for germanium is much higher than that of the corresponding silicon reaction. In a side-by-side experiment using SiO2 and GeO2 where the surface area of the silicon dioxide was 2 orders of magnitude higher than that of the GeO2, the base-catalyzed reaction with DMC was about an order of magnitude higher for the germanium dioxide. When GeO2 and 5% KOH were reacted with DMC at 350 °C, two products formed: (MeO)4Ge (70%) and MeGe(OMe)3 (30%). Confirmation of the identity of MeGe(OMe)3 was by GCMS, 1H and 13C NMR, and comparison to an authentic sample made by reaction of MeGeCl3 with NaOMe. Experiments to determine the mechanism of the direct formation of Ge-C from GeO2 ruled out participation from CO, H2, or carbon. The KOH-catalyzed reaction of other metal oxides was explored including B2O3, Ga2O3, TiO2, Sb2O3, SnO2, and SnO. Boron reacted to give unknown volatile products. Antimony reacted to give a solid which analyzed as Sb(OMe)3. SnO reacted with DMC to give a mixture that included (MeO)4Sn and possibly Me3Sn(OMe).
Synthesis and reactivity of a nickel(ii) thioperoxide complex: Demonstration of sulfide-mediated N2O reduction
Hartmann, Nathaniel J.,Wu, Guang,Hayton, Trevor W.
, p. 6580 - 6588 (2018)
The thiohyponitrite ([SNNO]2-) complex, [K(18-crown-6)][LtBuNiII(κ2-SNNO)] (LtBu = {(2,6-iPr2C6H3)NC(tBu)}2CH), extrudes N2 under mild heating to yield [K(18-crown-6)][LtBuNiII(η2-SO)] (1), along with minor products [K(18-crown-6)][LtBuNiII(η2-OSSO)] (2) and [K(18-crown-6)][LtBuNiII(η2-S2)] (3). Subsequent reaction of 1 with carbon monoxide (CO) results in the formation of [K(18-crown-6)][LtBuNiII(η2-SCO)] (4), [K(18-crown-6)][LtBuNiII(S,O:κ2-SCO2)] (5), [K(18-crown-6)][LtBuNiII(κ2-CO3)] (6), carbonyl sulfide (COS) (7), and [K(18-crown-6)][LtBuNiII(S2CO)] (8). To rationalize the formation of these products we propose that 1 first reacts with CO to form [K(18-crown-6)][LtBuNiII(S)] (I) and CO2, via O-atom abstraction. Subsequently, complex I reacts with CO or CO2 to form 4 and 5, respectively. Similarly, the formation of complex 6 and COS can be rationalized by the reaction of 1 with CO2 to form a putative Ni(ii) monothiopercarbonate, [K(18-crown-6)][LtBuNiII(κ2-SOCO2)] (11). The Ni(ii) monothiopercarbonate subsequently transfers a S-atom to CO to form COS and [K(18-crown-6)][LtBuNiII(κ2-CO3)] (6). Finally, the formation of 8 can be rationalized by the reaction of COS with I. Critically, the observation of complexes 4 and 5 in the reaction mixture reveals the stepwise conversion of [K(18-crown-6)][LtBuNiII(κ2-SNNO)] to 1 and then I, which represents the formal reduction of N2O by CO.
Hydrogen Sulfide Induced Carbon Dioxide Activation by Metal-Free Dual Catalysis
Kumar, Manoj,Francisco, Joseph S.
, p. 4359 - 4363 (2016)
The role of metal free dual catalysis in the hydrogen sulfide (H2S)-induced activation of carbon dioxide (CO2) and subsequent decomposition of resulting monothiolcarbonic acid in the gas phase has been explored. The results suggest that substituted amines and monocarboxylic type organic or inorganic acids via dual activation mechanisms promote both activation and decomposition reactions, implying that the judicious selection of a dual catalyst is crucial to the efficient C-S bond formation via CO2 activation. Considering that our results also suggest a new mechanism for the formation of carbonyl sulfide from CO2 and H2S, these new insights may help in better understanding the coupling between the carbon and sulfur cycles in the atmospheres of Earth and Venus. It's a gas, gas, gas: The role of metal-free dual catalysis in the hydrogen sulfide-induced activation of carbon dioxide has been explored by means of quantum chemical calculations. These results suggest a new mechanism for the formation of carbonyl sulphide in the atmospheres of Earth and Venus.
Mechanistic aspects of ketene formation deduced from femtosecond photolysis of diazocyclohexadienone, o-phenylene thioxocarbonate, and 2-chlorophenol
Burdzinski, Gotard,Kubicki, Jacek,Sliwa, Michel,Réhault, Julien,Zhang, Yunlong,Vyas, Shubham,Luk, Hoi Ling,Hadad, Christopher M.,Platz, Matthew S.
, p. 2026 - 2032 (2013)
The photochemistry of diazocyclohexadienone (1), o-phenylene thioxocarbonate (2), and 2-chlorophenol (3) in solution was studied using time-resolved UV-vis and IR transient absorption spectroscopies. In these three cases, the same product cyclopentadienyl ketene (5) is formed, and two different mechanistic pathways leading to this product are discussed: (a) rearrangement in the excited state (RIES) and (b) a stepwise route involving the intermediacy of vibrationally excited or relaxed carbene. Femtosecond UV-vis detection allows observation of an absorption band assigned to singlet 2-oxocyclohexa-3,5- dienylidene (4), and this absorption feature decays with an ～30 ps time constant in hexane and acetonitrile. The excess vibrational energy present in nascent carbenes results in the ultrafast Wolff rearrangement of the hot species. IR detection shows that photoexcited o-phenylene thioxocarbonate (2) and 2-chlorophenol (3) efficiently form the carbene species while diazocyclohexadienone (1) photochemistry proceeds mainly by a concerted process.
Degradation of an acetylene terminated sulfone (ATS) resin I. In an oxygen free environment
Stevenson,Goldfarb
, p. 2643 - 2665 (1990)
A study of the rates and mechanisms of degradation of an acetylene terminated sulfone resin, more precisely, bis[4-(3-ethynyl phenoxy) phenyl] sulfone and its higher oligomers, under high vacuum conditions, and under a flowing atmosphere of nitrogen, was
Progress toward colorimetric and fluorescent detection of carbonyl sulfide
Cerda, Matthew M.,Fehr, Julia M.,Sherbow, Tobias J.,Pluth, Michael D.
, p. 9644 - 9647 (2020)
We report here that a fluorescent benzobisimidazolium salt (TBBI) can be used for the fluorescent and colorimetric detection of carbonyl sulfide (COS) over related heterocumulenes including CO2 and CS2 in wet MeCN. The reaction between TBBI and COS in the presence of fluoride yields a highly fluorescent (λem = 354 nm) and colored product (λmax = 321, 621 nm), that is readily observed by the naked eye. We view these results as a first step toward developing activity-based probes for COS detection.
