463-58-1Relevant articles and documents
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Klemenc
, (1930)
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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
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.
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.
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.
Flueckiger
, p. 214 (1871)
Monothiocarbamates Strongly Inhibit Carbonic Anhydrases in Vitro and Possess Intraocular Pressure Lowering Activity in an Animal Model of Glaucoma
Vullo, Daniela,Durante, Mariaconcetta,Di Leva, Francesco Saverio,Cosconati, Sandro,Masini, Emanuela,Scozzafava, Andrea,Novellino, Ettore,Supuran, Claudiu T.,Carta, Fabrizio
, p. 5857 - 5867 (2016)
A series of monothiocarbamates (MTCs) were prepared from primary/secondary amines and COS as potential carbonic anhydrase (CA, EC 4.2.1.1) inhibitors, using the dithiocarbamates, the xanthates, and the trithiocarbonates as lead compounds. The MTCs effectively inhibited the pharmacologically relevant human (h) hCAs isoforms I, II, IX, and XII in vitro and showed KIs spanning between the low and medium nanomolar range. By means of a computational study, the MTC moiety binding mode on the CAs was explained. Furthermore, a selection of MTCs were evaluated in a normotensive glaucoma rabbit model for their intraocular pressure (IOP) lowering effects and showed interesting activity.
Wampler, F. B.,Horowitz, A.,Calvert, J. G.
, p. 5523 - 5532 (1972)
96: A Giant Self-Assembled Copper(I) Supramolecular Wheel Exhibiting Photoluminescence Tuning and Correlations with Dynamic Solvation and Solventless Synthesis
Gupta, Arvind K.,Kishore, Pilli V. V. N.,Cyue, Jhih-Yu,Liao, Jian-Hong,Duminy, Welni,Van Zyl, Werner E.,Liu
, p. 8973 - 8983 (2021)
The hierarchical self-organization of structurally complex high-nuclearity metal clusters with metallosupramolecular wheel architectures that are obtained from the self-Assembly of smaller solvated cluster units is rare and unique. Here, we use the potentially heteroditopic monothiocarbonate ligand and demonstrate for the first time the synthesis and structure of a solvated non-cyclic hexadecanuclear cluster [Cu{SC(O)OiPr}]16·2THF (1) that can simultaneously desolvate and self-Assemble in solution and subsequently form a giant metallaring, [Cu{SC(O)OiPr}]96 (2). We also demonstrate a luminescent precursor to cluster (2) can be achieved through a solventless and rapid mechanochemical synthesis. Cluster (2) is the highest nuclearity copper(I) wheel and the largest metal cluster containing a heterodichalcogen (O, S) ligand reported to date. Cluster (2) also exhibits solid-state luminescence with relatively long emission lifetimes at 4.1, 13.9 (μs). The synthetic strategy described here opens new research avenues by replacing solvent molecules in stable {Cu16} clusters with designed building units that can form new hybrid and multifunctional finite supramolecular materials. This finding may lead to the development of novel high-nuclearity materials self-Assembled in a facile manner with tunable optical properties.
Jones, B. M. R.,Burrows, J. P.,Cox, R. A.,Penkett, S. A.
, p. 372 - 376 (1982)
C-Nitrosothioformamide: A Donor Template for Dual Release of HNO and H2S
Kelly, Shane S.,Ni, Xiang,Radford, Miles N.,Xian, Ming,Yuen, Vivian
, (2022/04/12)
C-Nitrosothioformamide was demonstrated to be a donor template for dual release of HNO and COS triggered by a retro-Diels-Alder reaction. COS is an H2S precursor in the presence of carbonic anhydrase. This process produces HNO and H2S in a slow but steady manner. As such, the direct reaction between HNO and H2S under this situation appears to be minor. This may provide a useful tool for studying the synergistic effects of HNO and H2S.
Alkylamine-Substituted Perthiocarbamates: Dual Precursors to Hydropersulfide and Carbonyl Sulfide with Cardioprotective Actions
Khodade, Vinayak S.,Pharoah, Blaze M.,Paolocci, Nazareno,Toscano, John P.
supporting information, p. 4309 - 4316 (2020/03/05)
The recent discovery of hydropersulfides (RSSH) in mammalian systems suggests their potential roles in cell signaling. However, the exploration of RSSH biological significance is challenging due to their instability under physiological conditions. Herein, we report the preparation, RSSH-releasing properties, and cytoprotective nature of alkylamine-substituted perthiocarbamates. Triggered by a base-sensitive, self-immolative moiety, these precursors show efficient RSSH release and also demonstrate the ability to generate carbonyl sulfide (COS) in the presence of thiols. Using this dually reactive alkylamine-substituted perthiocarbamate platform, the generation of both RSSH and COS is tunable with respect to half-life, pH, and availability of thiols. Importantly, these precursors exhibit cytoprotective effects against hydrogen peroxide-mediated toxicity in H9c2 cells and cardioprotective effects against myocardial ischemic/reperfusion injury, indicating their potential application as new RSSH- and/or COS-releasing therapeutics.
