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A concise and practical strategy via potassium-carbonate-mediated [3 + 2]-cycloaddition reaction of α-halohydroxamates with the common solvent carbon disulfide for the synthesis of functionalized rhodanine derivatives in good to excellent yields is developed. The present methodology features a wide substrate scope as well as good functional group tolerance. The potential synthetic utility of this protocol is demonstrated by synthesis of a series of natural product derivatives containing rhodamine skeletons.

We present a new class of room-temperature stable diazoalkenes featuring a 1,2,3-triazole backbone. Dinitrogen of the diazoalkene moiety can be thermally displaced by an isocyanide and carbon monoxide. The latter alkylidene ketenes are typically considered as highly reactive compounds, traditionally only accessible by flash vacuum pyrolysis. We present a new and mild synthetic approach to the first structurally characterized alkylidene ketenes by a substitution reaction. Density functional theory calculations suggest the substitution with isocyanides to take place via a stepwise addition/elimination mechanism. In the case of carbon monoxide, the reaction proceeds through an unusual concerted exchange at a vinylidene carbon center. The vinylidene ketenes react with carbon disulfide via a four-membered thiete intermediate to give vinylidene thioketenes under release of COS. We present spectroscopic as well as structural data for the complete isoelectronic series (R2C═C═X; X = N2, CO, CNR, CS) including 1J(13C-13C) data. As N2, CO, and isocyanides belong to the archetypical ligands in transition-metal chemistry, this process can be interpreted in analogy to coordination chemistry as a ligand exchange reaction at a vinylidene carbon center.

A new approach for the annulation of a thiopyrane ring to an indole core under mild conditions was developed. Treating 2-methyl-3-acylindoles with lithium diisopropyl amide leads to the elimination of a proton from the 2-methyl group. The lithium indole-2,3-dienolates obtained were found to react with CS2 to give the corresponding thiopyrano[4,3-b]indole-3(5H)-thiones. The mechanism represents a stepwise addition through ion-pair formation, according to PCM/B3LYP/6-311++G**, PBE1PBE/6-311++G**, and MP2//HF/6-311++G** quantum chemical calculations. AIM calculations revealed the essential role of the Li atom at all stages of the process.

A transition-metal-free one-pot three-component annulation between diaryliodonium triflates, cyclic and acyclic aliphatic amines, and carbon disulfide providing a convenient and efficient access to biologically relevant S-aryl dithiocarbamates is developed. The reaction does not require metal, base, or any other additive and operates under mild and ambient conditions. This methodology is robust, scalable, and exhibits a broad substrate scope. The in silico analysis revealed that the majority of the compounds have a drug-likeness and good ADMET characteristics.

Carbon disulfide is an archetypal double-bonded molecule belonging to the class of group IV-group VI, AB2 compounds. It is widely believed that, upon compression to several GPa at room temperature and above, a polymeric chain of type (-(C═S)-S-)n, named Bridgman's black polymer, will form. By combining optical spectroscopy and synchrotron X-ray diffraction data with ab initio simulations, we demonstrate that the structure of this polymer is different. Solid molecular CS2 polymerizes at ∼10-11 GPa. The polymer is disordered and consists of a mixture of 3-fold (C3) and 4-fold (C4) coordinated carbon atoms with some C═C double bonds. The C4/C3 ratio continuously increases upon further compression to 40 GPa. Upon decompression, structural changes are partially reverted, while the sample also undergoes partial disproportionation. Our work uncovers the nontrivial high-pressure structural evolution in one of the simplest molecular systems exhibiting molecular as well as polymeric phases.

Regenerated cellulose fibers represent an important class of bioderived commercial fibers. The traditional viscose process requires the use of environmentally harmful carbon disulfide solvent to pr...

Hanglaiwan subbituminous coal (HSBC) was subjected to solvent extraction (SE) with an isometric carbon disulfide/acetone mixed solvent (IMCDSAMS) to obtain a residue (RSE). Thermal dissolution (TD)...

Natural gas liquids can contain varying amounts of sulfur impurities that can impact thermophysical and thermochemical properties even after separation through liquefaction. Reference quality equat...

Thiophosphorus acids R1R2P(S)OH constitute an important class of organophosphorus compounds, in which the phosphorus atom is intrinsically chiral if R1 ≠ R2. In connection with a project aimed at the preparation of chiral thiophosphorus acids, various available literature methods were considered, but few fit the requirement of odorless reagents. Herein, the results of our studies on the synthesis of thiophosphinic acids are reported. Ultimately, two major approaches were selected: (1) the Stec reaction of phosphorus amides with carbon disulfide; and (2) the one-pot synthesis of thiophosphorus acids from H-phosphinates, an organometallic nucleophile, and quenching with elemental sulfur. An application to the preparation of a potential chiral phosphorus organocatalyst is also reported.

A phenyl-substituted macrocyclic π-extended thiophene hexamer 1, composed of four thienylene-ethynylene and two thienylene-vinylene units, has a solid-state structure in which π–π, CH−π, and van de...

A covalent sulfur–carbon (covalent-SC) composite is successfully prepared in situ by a wet-chemical solvothermal method based on the strong interaction between carbon disulfide (CS2) and red phosph...

Utilization of carbon disulfide (CS2), a low-cost and sulfur-rich one-carbon (C1) feedstock, for making sulfur-containing polymers is important for both polymer chemistry and applied environmental ...

Efficient analytical representations of the thermodynamic properties for carbon disulfide remain open challenges in the communality of science and engineering. We present two analytical representations of the entropy and Gibbs free energy for gaseous carbon disulfide which we find to be of satisfactory accuracy and convenient for future use. The proposed two analytical representations merely rely on five molecular constants of the carbon disulfide molecule and avoid applications of a large number of experimental spectroscopy data. In the temperature range from 300 to 6000 K, the average relative deviations of the predicted molar entropy and reduced Gibbs free energy values from the National Institute of Standards and Technology database are 0.250 and 0.108%, respectively.

This is the first time that the amidato lanthanide amides ({L nLn[N(SiMe3)2]THF}2 ( n = 1, Ln = Eu (1); n = 2, Ln = Eu (3), Yb (4); HL1 = tBuC6H4CONHC6H3( iPr)2; HL2 = C6H5CONHC6H3( iPr)2) and {L3Eu[N(SiMe3)2]THF}{L32Eu(THF)2} (2) (HL3 = ClC6H4CONHC6H3( iPr)2)) were applied in the cycloaddition reactions of aziridines with carbon dioxide (CO2) or carbon disulfide (CS2) under mild conditions. The corresponding oxazolidinones and thiazolidine-2-thiones were obtained in good to excellent yields with good functional group tolerance.

As important active sites of oxidoreductase in mitochondria, selenocysteine (Sec) takes the responsibility for cytoprotective effect and intracellular redox homeostasis. Carbon disulfide (CS2) is a common solvent in industry, which can inhibit the activities of oxidoreductase and induce oxidative stress. It is necessary to investigate the cytoprotective effect of Sec against CS2 exposure. After integrated, the response moiety 2,4-dinitrobenzenesulfonamide and mitochondrial targeting moiety into the near-infrared heptamethine cyanine fluorophore, we develop a mitochondrial targeting near-infrared ratiometric fluorescent probe Mito-diNO2 for the selective and sensitive analysis of Sec concentration fluctuations in living cells and in mice models under the stimulation of CS2. The probe can effectively accumulate in mitochondria and selectively detect the endogenous Sec concentrations in BRL 3A, RH-35, HL-7702, HepG2, and SMMC-7721 cell lines. The results indicate that CS2 exposure can lead to a decrease of Sec level and result in mitochondrial related acute inflammation. The exogenous supplement of Sec can protect cells from oxidative damage and reduce the symptoms of inflammation. We also establish CS2 induced acute and chronic hepatitis mice models to examine the tissue toxicity of CS2 and cytoprotection of Sec in liver. The organism can increase the concentration of Sec to deal with the damage caused by CS2 in acute hepatitis mice model. Also the exogenous supplement of Sec for the two mice models can effectively defend the CS2 induced liver damage. The real-time imaging of Sec concentrations in liver can be used to assess the degrees of liver injury during CS2 poisoning. The above applications make our probe a potential candidate for the clinical accurate diagnosis and treatment of CS2 poisoning.

The synthesis of cyclic thiocarbonates by the cycloaddition of carbon disulfide (CS2) to thiiranes in the presence of silica-immobilized amine catalysts was investigated. The catalytic activities of the silica-immobilized catalysts toward the synthesis of cyclic thiocarbonates were higher than the activities of their homogeneous counterparts. The silica-supported catalysts strongly accelerated the cycloaddition of CS2 to thiiranes, and the pseudo-first-order rate constant of the silica-immobilized catalyst was about 430 times larger than that of the corresponding homogeneous catalyst. The coexistence of the molecular catalyst species and the neighboring surface silanols on the catalyst support was found to be key to the reaction acceleration. In addition to providing improved catalytic activity, the solid-supported catalysts were also shown to be recyclable and reusable for at least five cycles.

One-dimensional (1D) single-crystalline hexagonal nanorods of Lu2@C3v(8)–C82 were prepared for the first time using the liquid–liquid interface precipitation (LLIP) method from the interfaces between carbon disulfide (CS2) and isopropyl alcohol (IPA). The length of the nanorods can be readily controlled by varying the concentration of the Lu2@C82 solution in addition to the volume ratio of CS2 to IPA. The latter factor also exhibits a significant influence on the morphology of the crystals. The crystalline structure of the nanorods has been investigated by XRD and selected area electron diffraction (SAED), suggesting a face-centered cubic structure. Photoluminescence of the Lu2@C82 nanorods shows a remarkable enhancement as compared to that of pristine Lu2@C82 powder because of the high crystallinity. Furthermore, we have investigated the photoelectrochemical properties of Lu2@C82 nanorods, proving their potential applications as photodetectors.

A series of ion-exchanged zeolites Y were prepared by postsynthesis method and characterized using multiple techniques including XRD, N2 adsorption, XPS, FTIR, and chemical composition analysis. The adsorption of carbon disulfide (CS2) on ion-exchanged zeolites Y was investigated by dynamic adsorption tests carried out at a fixed-bed adsorption unit coupled with density functional theory (DFT) computation. The effects of metal ions, gas hourly space velocity (GHSV), and operation temperature on the adsorption capacities of CS2 on ion-exchanged samples were studied carefully. In addition, the mechanism for CS2 adsorption on zeolite Y was discussed. Among all the ion-exchanged samples, Ag–Y zeolite holds the highest CS2 breakthrough adsorption capacity up to 44.8 mg/g. The XPS analysis indicates that Ag+ was introduced into the zeolite Y structure. The DFT study indicates that the S–M (σ) bond involving CS2 and Ag+ was formed, which strengthens the S–Ag interaction and, therefore, benefits the adsorption of...

Development of lithium sulfur (Li–S) batteries with high Coulombic efficiency and long cycle stability remains challenging due to the dissolution and shuttle of polysulfides in electrolyte. Here, a novel additive, carbon disulfide (CS2), to the organic electrolyte is reported to improve the cycling performance of Li–S batteries. The cells with the CS2-additive electrolyte exhibit high Coulombic efficiency and long cycle stability, showing average Coulombic efficiency >99% and a capacity retention of 88% over the entire 300 cycles. The function of the CS2 additive is 2-fold: (1) it inhibits the migration of long-chain polysulfides to the anode by forming complexes with polysulfides and (2) it passivates electrode surfaces by inducing the protective coatings on both the anode and the cathode.

Carbon sulfides are known as a class of binary compounds that can exist in various isomeric and/or polymeric forms. As for a sulfur-rich compound with the composition formula CS3, two possible constitutional isomers have been proposed experimentally or theoretically for the neutral species and its corresponding radical cation and anion. Although the previous studies claim that one isomer has a carbon trisulfide (CS3) C-centered configuration and the other has a carbon disulfide S-sulfide (SCSS) chain configuration, they have not yet been fully identified by a spectroscopic method. In this study, we have prepared the anions of those isomers in the gas phase by employing two types of reactions: dissociative electron attachment to 1,3-dithiole-2-thione for CS3(-) formation and the S(-) + CS2 ion-molecule reaction for SCSS(-). Photoelectron spectroscopic measurements reveal that the reactions result in the production of two anionic species that can be well distinguished by their vertical detachment energy. With the aid of ab initio calculations, they are identified distinctively as the anions of carbon trisulfide and carbon disulfide S-sulfide.

An efficient one-pot, four-component reaction for the synthesis of dithiocarbamates using carbon disulfide, cyclic imines, acid chlorides, and commercially available primary or secondary amines has been developed by performing an acid chloride addition to a heterocyclic imine followed by subsequent nucleophilic substitution of in situ generated dithiocarbamic acid. With the aid of the newly developed and powerful multicomponent reaction, a direct route for the synthesis of 24 unknown dithiocarbamates in moderate to good yield under mild conditions is enabled.

The synthesis of highly regioregular and alternating polythiocarbonates from carbon disulfide and terminal epoxides has been achieved. The copolymerizations were performed under ambient and solvent-free conditions in the presence of LiOtBu (0.125–0.5 mol %) as initiator. At higher loadings the reaction pathway switched in favor to the catalytic formation of cyclic dithiocarbonates. Under optimized reaction conditions polymers with molecular weights up to 109 kg mol–1 were isolated. The NMR spectroscopic analysis of the polythiocarbonates revealed that 94% of backbone structure is formed by strongly alternating head-to-head arrangement of epoxypropane and 1,2-epoxybutane monomers, respectively, at a thiocarbonate group −CHR–OC(S)O–CHR– and tail-to-tail arrangement at a trithiocarbonate group −CH2–SC(S)S–CH2–. Atactic polymers were obtained using racemic mixtures of the epoxides, but an isotactic polymer was obtained when chiral (R)-epoxypropane was converted. A mechanism is proposed which rationalizes the ...

Reduced graphene oxide (rGO) served as a green catalyst with ambient oxygen as a clean oxidant for dearomatizing cyclizations of naphthol Mannich bases with carbon disulfide under mild conditions. Notably, this process provides novel and efficient one-pot access to spiro thiazolidinethione compounds. Fourier transform infrared analysis, transmission electron microscopy, atomic force microscopy, X-ray photoelectron microscopy, thermogravimetric analysis, Raman analysis, and X-ray diffraction were used to characterize rGO. And, the rGO can be reused at least six times without significant loss of catalytic activity. A possible reaction mechanism was proposed. In addition, some target compounds showed inhibition against Sclerotinia sclerotiorum, Botrytis cinerea, Thanatephorus cucumeris, and other fungi.

The reaction of isolable dialkylstannylene 1 with an excess amount of CS2 produces an isomeric mixture of 3,3′-distanna-2,2′,4,4′-tetrathiabicyclobutylidene 8 and 3,7-distanna-2,4,6,8-tetrathiabicyclo[3.3.0]oct-1(5)-ene 9 with a ratio depending on the reaction conditions. Compounds 8 and 9 are separated by column chromatography and characterized by NMR spectroscopy and X-ray crystallography. Detailed investigation of the reaction has revealed that the initial product is 8, which isomerizes to 9 irreversibly under the catalytic influence of 1 as a Lewis acid. The above view is supported by the theoretical DFT calculations. Treatment of 1 with ArN═C═O [Ar = 2,6-iPr2C6H3] affords the corresponding carbamoyl(hydroxyl)stannane 11 via the hydrolysis of the corresponding silaaziridinone formed by the [1 + 2] cycloaddition reaction of 1 with the N═C double bond of the isocyanate. Stannylene 1 reacts with ArN═C═S, giving a mixture of complex products, while 1 does not react with CO2.

Over one million tons of carbon disulfide are produced globally each year for an array of applications, and emissions of this highly volatile and toxic liquid, known to generate acid rain, remain poorly controlled. As such, materials capable of reversibly capturing this commodity chemical in an energy-efficient manner are of interest. Recently, we detailed a family of diamine-appended metal–organic frameworks capable of selectively capturing carbon dioxide through a cooperative insertion mechanism that promotes efficient adsorption–desorption cycling. We therefore sought to explore the fundamental ability of these materials to capture CS2 through a similar mechanism. Employing crystallography, spectroscopy, and gas adsorption analysis, we demonstrate that CS2 is indeed cooperatively adsorbed in N,N-dimethylethylenediamine-appended M2(dobpdc) (M = Mg, Mn, Zn; dobpdc4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate), via the formation of electrostatically paired ammonium dithiocarbamate chains. Notably, in the weakly thiophilic Mg congener, chemisorption is cleanly reversible with mild thermal input. Importantly, this work demonstrates that the hitherto CO2-specific cooperative insertion mechanism can be generalized to other high-impact target molecules.

The catalytic coupling of oxetane, the symmetric isomer of propylene oxide, with carbon disulfide has been investigated utilizing (salen)CrCl in the presence of various onium salts. Oxygen and sulfur atom exchange was observed in both the polymeric and cyclic carbonate products. The coupling of oxetane and CS2 was selective for copolymer formation over a wide range of reaction conditions. Five different polymer linkages and two cyclic products were determined by 1H and 13C NMR spectroscopy, and these results were consistent with in situ infrared spectroscopic monitoring of the process. The major cyclic product produced in the coupling process was trimethylene trithiocarbonate, which was isolated and characterized by single crystal X-ray crystallography. Upon increasing the CS2/oxetane feed ratio, a decrease in the O/S scrambling occurred. The reaction temperature had the most significant effect on the O/S exchange process, increasing exchange with increasing temperature. The presence of the onium salt ini...

New insight into the complexity of the reaction of the prominent catalyst RuCl2(PPh3)3 with carbon disulfide has been obtained from a combination of X-ray diffraction and (31)P NMR studies. The red-violet compound originally formulated as a cationic π-CS2 complex, [RuCl(π-CS2)(PPh3)3]Cl, has been identified as a neutral molecule, RuCl2(S2CPPh3)(PPh3)2, which contains the unstable zwitterion S2CPPh3. In the absence of RuCl2(PPh3)3, there is no sign of a reaction between triphenylphosphine and carbon disulfide, although more basic trialkylphosphines form red adducts, S2CPR3. Despite the presence of an unstable ligand, RuCl2(S2CPPh3)(PPh3)2 is remarkably stable. It survives melting at 173-174 °C intact, is stable to air, and undergoes reversible electrochemical oxidation to form a monocation. When the reaction of RuCl2(PPh3)3 with carbon disulfide is conducted in the presence of methanol, crystals of orange [RuCl(S2CPPh3)(CS)(PPh3)2]Cl·2MeOH and yellow RuCl2(CS)(MeOH)(PPh3)2 also form. (31)P NMR studies indicate that the unsymmetrical dinuclear complex (SC)(Ph3P)2Ru(μ-Cl)3Ru(PPh3)2Cl is the initial product of the reaction of RuCl2(PPh3)3 with carbon disulfide. A path connecting the isolated products is presented.

We report the reactions of several heteroallenes (carbon disulfide, carbonyl sulfide, and phenyl isocyanate) and carbon monoxide with a three-coordinate, bis(phosphine)-supported Rh(I) disilylamide (1). Carbon disulfide reacts with 1 to afford a silyltrithiocarbonate complex similar to an intermediate previously invoked in the deoxygenation of CO2 by 1, and prolonged heating affords a structurally unusual μ-κ(2)(S,S'):κ(2)(S,S')-trithiocarbonate dimer. Carbonyl sulfide reacts with 1 to afford a structurally unique Rh(SCNCS) metallacycle derived from two insertions of OCS and N-to-O silyl-group migrations. Phenyl isocyanate reacts with 1 to afford a dimeric bis(phenylcyanamido)-bridged complex resulting from multiple silyl-group migrations and nitrogen-for-oxygen metathesis, akin to reactivity previously observed with carbon dioxide. The ability of 1 to activate carbon-chalcogen multiple bonds via silyl-group migration is further supported by its reactivity with carbon monoxide, where a nitrogen-for-oxygen metathesis is also observed with expulsion of hexamethyldisiloxane. For all reported reactions, intermediates are observable under appropriate conditions, allowing the formulation of mechanisms where insertion of the unsaturated substrate is followed by one or more silyl-group migrations to afford the observed products. This rich variety of reactivity confirms the ability of metal silylamides to activate exceptionally strong carbon-element multiple bonds and suggests that silylamides may be useful intermediates in nitrogen-atom and nitrene-group-transfer schemes.

We report the results of our investigation on the electron spin relaxation mechanism of the monoanion of C60 fullerene in liquid solution. The solvent chosen was carbon disulfide, which is rather uncommon in EPR spectroscopy but proved very useful here because of its liquid state over a wide temperature range. The conditions for exclusive formation of the monoanion of C60 in CS2 were first determined using electrochemical measurements. Using these results, only the monoanion of C60 was prepared by chemical reduction using Hg2I2/Hg as the reducing agent. The EPR line width was measured over a wide temperature range of 120-290 K. The line widths show weak dependence on temperature, changing by a factor of only about 2, over this temperature range. We show that the observed temperature dependence does not obey the Kivelson-Orbach mechanism of electron spin relaxation in liquids, applicable for radicals with low-lying, thermally accessible excited electronic states. The observed temperature dependence can be empirically fitted to an Arrhenius type of exponential function, from which an activation energy of 74 ± 3 cm(-1) is obtained. From the qualitative similarities in the characteristics of the spin relaxation rates of C60 monoanion radical and the cyclohexane type of cation radicals reported in the literature, we propose that a pseudorotation-induced electron spin relaxation process could be operating in the C60 monoanion radical in liquid solution. The low activation energy of 74 cm(-1) observed here is consistent with the pseudorotation barrier of C60 monoanion, estimated from reported Jahn-Teller energy levels.

Five potential charge transfer complexes of trimeric perfluoro-o-phenylene mercury (I) with tetrathiafulvalene (TTF) and tetramethyltetraselenefulvalene (TMTSF) were grown from different solvent mixtures. The adducts (I)2·TTF (1) and I·TTF (2) were grown by slow evaporation from the 1:1 mixture of dichloromethane (CH2Cl2, DCM) and carbon disulfide (CS2). Use of the different 1:1 solvent mixtures of dichloromethane (CH2Cl2, DCM) and dichloroethane (C2H4Cl2, DCE) has led to the crystalline adducts I·TTF (3) and I·TTF·DCE (4). Adduct I.TMTSF (5) was grown by the interface crystallization on the border of two immiscible layers, ethyl acetate, and carbon disulfide. The cocrystals differ by the donor–acceptor ratio, molecular packing, and the solvent inclusion. The components in 1–5 form mixed donor–acceptor stacks. The stacks are stabilized by Hg···S and Hg···C short contacts, while the lateral interactions between stacks include F···F, CH···F, and S/Se···F short contacts.

Experimental data for the unimolecular decomposition of CS2 from the literature are analyzed by unimolecular rate theory with the goal of obtaining rate constants for the reverse reaction S + CS (+M) → CS2 (+M) over wide temperature and pressure ranges. The results constitute an important input for the kinetic modeling of CS2 oxidation. CS2 dissociation proceeds as a spin-forbidden process whose detailed properties are still not well understood. The role of the singlet-triplet transition involved is discussed.

The aza-crown ether compounds 1-aza-15-crown-5 and 1,10-diaza-18-crown-6 react with sodium hydroxide and carbon disulfide to provide the dithiocarbamates [15]aneO4-NCS2Na and NaS2CN-[18]aneO4-NCS2Na in good yield. The complexes [MRCl(CO)(L)(PPh3)2] (M = Ru, R = H, CH═CHC6H4Me-4, CH═CHBut, CH═CH-pyrenyl-1, C(C≡CPh)═CHPh; M = Os, R = H, CH═CH-pyrenyl-1; L = 2,1,3-benzothiadiazole or no ligand) undergo reaction with [15]aneO4-NCS2Na and NaS2CN-[18]aneO4-NCS2Na to yield [MR(S2CN-[15]aneO4)(CO)(PPh3)2] and [{MR(CO)(PPh3)2}2(S2CN-[18]aneO4-NCS2)], respectively. In a similar manner, cis-[RuCl2(dppm)2] provides [Ru(S2CN-[15]aneO4)(dppm)2]+ and [{Ru(dppm)2}2(S2CN-[18]aneO4-NCS2)]2+, respectively. Reaction of [Ru(CH═CHC6H4Me-4)(S2CN-[15]aneO4)(CO)(PPh3)2] with excess HC≡CBut leads to the formation of the alkynyl complex [Ru(C≡CBut)(S2CN-[15]aneO4)(CO)(PPh3)2]. Treatment of [OsHCl(CO)(BTD)(PPh3)2] with [HC≡C-bpyReCl(CO)3] results in the bimetallic compound [Os{CH═CH-bpyReCl(CO)3}Cl(CO)(BTD)(PPh3)2]. This reacts with...

Dithiocarboxylic acids, RCS2H, and their esters, RCS2R′, are useful reagents that can be synthesized by the reaction of carbon disulfide with organometallic reagents. Here the coinage-metal-mediated transformation of acetate to dithioacetate is explored in the gas phase using multistage mass spectrometry experiments in a linear ion trap mass spectrometer in conjunction with density functional theory (DFT) calculations. The ion–molecule reactions between coinage-metal dimethylmetalate anions [CH3MCH3]− (M = Au, Ag, Cu), formed via double decarboxylation of the metal acetate anions, [CH3CO2MO2CCH3]−, and carbon disulfide, were examined. Only [CH3CuCH3]− reacts with CS2 with a reaction efficiency of 0.8% of the collision rate to yield the adduct [CH3CuS2CCH3]− (77.5%) as well as CH3CS2– (22.5%). Collision-induced dissociation (CID) of the adduct [CH3CuS2CCH3]− gives CH3CS2– as the major product, with a small amount of [CuS2CCH2]− being formed via loss of methane. DFT calculations reveal the following. (i) [C...

The sequestration of carbon disulfide (CS2), a common pollutant in environmental systems, is of great importance due to its physical harm to human beings. Compared with CO2 capture, that of CS2 is much less developed. The use of P/N-based frustrated Lewis pairs (FLPs) has been proven, both experimentally and theoretically, to be an alternative strategy to efficiently sequestrate CO2. Therefore, we pose the question of whether the analogue CS2 could also be sequestrated by the same FLPs, given that the C═S bond in CS2 is weaker than the C═O bond in CO2. Herein, we carry out a thorough DFT study to theoretically examine this hypothesis for a series of P/N-based FLPs. Our results reveal unexpectedly higher reaction barriers in CS2 capture by most of the P/N-based FLPs, although the bond dissociation energy of the C═S bond in CS2 (105.3 kcal mol–1) is smaller than that of the C═O bond in CO2 (127.2 kcal mol–1). The unexpected higher energy required for CS2 activation can be rationalized by its larger bond dis...

The trivalent uranium phenylchalcogenide series, Tp*2UEPh (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate, E = O (1), S (2), Se (3), Te (4)), has been synthesized to investigate the nature of the U-E bond. All compounds have been characterized by (1)H NMR, infrared and electronic absorption spectroscopies, and in the case of 4, X-ray crystallography. Compound 4 was also studied by SQUID magnetometry. Computational studies establish Mulliken spin densities for the uranium centers ranging from 3.005 to 3.027 (B3LYP), consistent for uranium-chalcogenide bonds that are primarily ionic in nature, with a small covalent contribution. The reactivity of 2-4 toward carbon disulfide was also investigated and showed reversible CS2 insertion into the U(III)-E bond, forming Tp*2U(κ(2)-S2CEPh) (E = S (5), Se (6), Te (7)). Compound 5 was characterized crystallographically.

Cocrystallization of diiodine and carbon disulfide with the two common fullerenes, C60 and C70, has been examined. The binary cocrystal, C70·I2, readily formed when a solution of diiodine in diethyl ether was layered over C70 dissolved in toluene, chlorobenzene, or 1,2-dichlorobenzene, but no binary cocrystal of diiodine and C60 could be obtained despite persistent efforts. The ternary cocrystal, C70·0.85I2·0.15CS2, which was grown from a carbon disulfide solution of C70 and a benzene solution of diiodine, is isostructural with C70·I2 but has 15% of the diiodine sites replaced with carbon disulfide. In contrast, C70·0.68I2·0.32CS2, which was obtained from diffusion of a cyclohexane solution of diiodine into a carbon disulfide solution of C70, is a unique ternary cocrystal that is not related to any binary cocrystal of C70 with diiodine or carbon disulfide. Crystals of 2C60·2.46CS2·0.54I2 were obtained from a saturated carbon disulfide solution of diiodine and C60. Black crystals of 2C60·2.46CS2·0.54I2 for...

Removal efficiency of CS2 (carbon disulfide) by activated carbon modified with different impregnants has been studied under micro-oxygen conditions. It was found that adsorbent ACCu-CoSPc-Ce possesses markedly enhanced adsorption purification ability. Reaction temperature and oxygen concentration were found to be crucial factors for the adsorption purification processes, and 60 °C as well as 2.0% oxygen seem to be the optimal conditions for CS2 removal. The structure of activated carbon samples and reaction mechanism were closely examined by a number of characterization techniques as follows: N2-BET (N2 adsorption/desorption), XRD (X-ray powder diffraction), XPS (X-ray photoelectron spectroscopy), SEM-EDS (scanning electron microscopy–electron diffraction spectroscopy), and CO2-TPD (temperature-programmed desorption of CO2). Presumably, large quantities of SO42– could be formed in the reaction process and then strongly adsorbed. SO2, CS2, and COS were detected in the effluent gas generated from ACCu-CoSPc...

Vapor–liquid equilibrium (VLE) measurements have been performed on several binary systems incorporating chemicals of interest to the biofuels industry. Systems were chosen based on two criteria: (1) similarity to measurement requests received by Wiltec and (2) suitability of using the Wilson Equation to model the activity coefficients for the VLE data. The Wilson Equation is a good choice for modeling fully miscible solutions of moderately polar compounds. With these two ideas in mind, systems were chosen incorporating the following compounds: 1-methoxy-2-propanol, 2-furaldehyde, allyl alcohol, butyl acetate, carbon dioxide, carbon disulfide, carbonyl sulfide, ethanolamine, ethyl acetate, n-butanol, pentane, and tert-butanol. Measurement temperatures ranged from −25 °C to +200 °C.

Xianfeng lignite (XL) was sequentially extracted under ultrasonication at room temperature with petroleum ether, carbon disulfide (CDS), methanol, acetone, and isometric CDS/acetone mixed solvent to afford extracts 1–5, respectively. The mixed solvent-inextractable portion was sequentially extracted with cyclohexane, benzene, 1-methylnaphthalene, methanol, and ethanol at 320 °C to afford extracts 6–10, respectively. The extracts were analyzed with a gas chromatography/mass spectrometer (GC/MS) to characterize biomarkers in XL. The biomarkers were significantly enriched in extracts 1 and 6. They can be classified into a series of n-alkanes, isoprenoid alkanes, terpenoids, n-alkenes, methyl alkanones, n-alkylbenzenes, n-alkyltoluenes, and n-alkyl-p-xylenes. The biomarker distributions provided important information on the main origin of organic matter in XL. Related mechanisms for the formation of biomarkers during coalification were discussed. The residue from sequential thermal extraction was subjected to...

The catalytic coupling of cyclopentene oxide with carbon disulfide has been investigated utilizing (salen)CrCl in the presence of added onium salts. Both polymeric and cyclic materials were produced, with oxygen/sulfur atom scrambling observed in both instances. This atom redistribution process was found to require (salen)CrCl and excess epoxide, though an increase in the rate of atom scrambling was noted upon the addition of the onium salt. Cyclopentene sulfide was observed as a side product of the coupling reaction and was found to be unreactive toward both CS2 and CO2, instead undergoing desulfurization to cyclopentene under the conditions of the reaction. Of the 12 cyclic cyclopentene [thio]carbonates possibly produced by this coupling reaction, eight were observed, and the crystal structure of trans-cyclopentene trithiocarbonate is reported herein. Computational studies reveal that the cis- cyclic materials are more stable than their trans-counterparts by >5 kcal/mol of enthalpy, and there is a 10–25...

Ruthenium carbene catalysts are able to catalyze crossed [2+2+2] cyclotrimerizations of α,ω-diynes with isocyanates, isothiocyanates, and carbon disulfide. Both aliphatic and aromatic isocyanates can be used to produce fused 2-pyridones, although aliphatic isocyanates were more reactive. Aromatic isocyanates give better results when they bear electron-donating substituents. The reaction of unsymmetrical α,ω-diynes gave a product only with the substituent adjacent to the 2-pyridone nitrogen. Isothiocyanates gave thiopyranimines upon reaction with the C═S bond, whereas CS2 reacted efficiently to give a thioxothiopyrane.

The structures of three crystalline solvates, D5h(1)-C90·CS2, D5h-C70·3CS2, and 2(D5h-C70)·3CS2, of nanotubular fullerenes have been determined by single crystal X-ray diffraction. Despite the marked tendency for fullerenes to disorder, the carbon cages in all three structures are fully ordered at 100(2) K for D5h(1)-C90·CS2 and 90 K for the other two crystals. Moreover, the carbon disulfide molecules are also ordered, except for the case of D5h(1)-C90·CS2, where there is a minor disorder in the solvate location. The molecular packing in D5h(1)-C90·CS2 reflects the nanotubular nature of the fullerene component with channels of alternating fullerenes and carbon disulfide molecules running along the crystallographic b axis. The molecular packing arrangements for D5h-C70·3CS2 and 2(D5h-C70)·3CS2 do not show such channels. In D5h-C70·3CS2, the carbon disulfide molecules form chains that snake between the fullerenes and along the crystallographic a axis. In 2(D5h-C70)·3CS2, there are two crystallographically d...

The methanol-insoluble portions from supercritical methanolysis of Shengli lignite (SL) and Huolinguole lignite (HL) were extracted with an isometric carbon disulfide/acetone mixed solvent under ultrasonic irradiation to afford extracts and extraction residues (ERs). The ERs were subjected to ruthenium-ion-catalyzed oxidation, and soluble portions were separated from the reaction mixture and esterified. The resulting products were analyzed with a gas chromatography/mass spectrometer and atmospheric solids analysis probe/time-of-flight mass spectrometer to reveal structural features of heavy species in the two lignites. The results show that the ER from SL is richer in highly condensed aromatic species than that from HL, while both ERs have the same carbon number range (C9–C24) of alkyl groups with the highest content at C15 on aromatic rings and the same distribution of alkylene bridges (C2–C20) connecting aromatic rings with a higher abundance of shorter linkages than that of longer linkages.

Geting bituminous coal (GBC) was sequentially extracted with petroleum ether, carbon disulfide (CDS), methanol, acetone, and isometric CDS/acetone mixed solvent at room temperature to afford extracts 1–5 (E1–E5) and residue. Detailed characterizations of the extracts were performed with a gas chromatography/mass spectrometer (GC/MS), Fourier transform infrared (FTIR) spectrometer, and direct analysis in real-time ionization source (DARTIS) coupled to an ion-trap mass spectrometer (ITMS). GBC and its residue were also analyzed with the FTIR spectrometer. Particle sizes of the residue were significantly reduced compared to those of GBC according to the observation with a scanning electron microscope. Arenes with 1–4 rings and more condensed arenes were enriched into E1 and E2, respectively, while more heteroatom-containing organic species were detected in other extracts, especially in E3 and E4 according to GC/MS analysis. The extracts, especially E1–E4, contain more aliphatic moieties and less aromatic moi...

Graphene-sulfur (G-S) hybrid materials with sulfur nanocrystals anchored on interconnected fibrous graphene are obtained by a facile one-pot strategy using a sulfur/carbon disulfide/alcohol mixed solution. The reduction of graphene oxide and the formation/binding of sulfur nanocrystals were integrated. The G-S hybrids exhibit a highly porous network structure constructed by fibrous graphene, many electrically conducting pathways, and easily tunable sulfur content, which can be cut and pressed into pellets to be directly used as lithium-sulfur battery cathodes without using a metal current-collector, binder, and conductive additive. The porous network and sulfur nanocrystals enable rapid ion transport and short Li(+) diffusion distance, the interconnected fibrous graphene provides highly conductive electron transport pathways, and the oxygen-containing (mainly hydroxyl/epoxide) groups show strong binding with polysulfides, preventing their dissolution into the electrolyte based on first-principles calculations. As a result, the G-S hybrids show a high capacity, an excellent high-rate performance, and a long life over 100 cycles. These results demonstrate the great potential of this unique hybrid structure as cathodes for high-performance lithium-sulfur batteries.

Dithiocarbamates (DTCs) were recently discovered as carbonic anhydrase (CA, EC 4.2.1.1) inhibitors. A series of xanthates and a trithiocarbonate, structurally related to the DTCs, were prepared by reaction of alcohols/thiols with carbon disulfide in the presence of bases. These compounds were tested for the inhibition of four human (h) isoforms, hCA I, II, IX, and XII, involved in pathologies such as glaucoma (CA II and XII) or cancer (CA IX). Several low nanomolar xanthate/trithiocarbonate inhibitors targeting these CAs were detected. A docking study of some xanthates within the CA II active site showed that these compounds bind in a similar manner with the dithiocarbamates, coordinating monodentately to the Zn(II) ion from the enzyme active site. Several xanthates showed potent intraocular pressure lowering activity in two animal models of glaucoma via the topical administration. Xanthates and thioxanthates represent two novel, promising classes of CA inhibitors.

We are developing bimetallic platforms for the cooperative activation of heteroallenes. Toward this goal, we designed a new family of bis(iminopyridine) ((N,N′-1,1′-(1,4-phenylene)bis(N-(pyridin-2-ylmethylene)methanamine) and N,N′-1,1′-(1,4-phenylene)bis(N-(1-(pyridin-2-yl)ethylidene)methanamine)) dinickel complexes, synthesized their CS2 compounds, and studied their reactivity. Bis(iminopyridine) ligands L react with Ni(COD)2 to form Ni2(L)2 complexes or Ni2(L)(COD)2 complexes as a function of the steric and electronic properties of the ligand precursor. Product structures disclosed an anti geometry in the Ni2(L)(COD)2 species and helical (anti) structures for Ni2(L)2 complexes. Carbon disulfide adducts Ni2(L)(CS2)2 were obtained in good yields upon addition of CS2 to Ni2(L)(COD)2 or in a one-pot reaction of L with 2 equiv of both Ni(COD)2 and CS2. Ni2(L)(CS2)2 complexes are highly flexible, displaying both syn and anti conformations (shortest S- - -S separations of 5.0 and 9.5 A, respectively) in the so...

Doping of graphene with heteroatoms is an effective way to tailor its properties. Here we describe a simple and scalable method of doping graphene lattice with sulfur atoms during the thermal exfoliation process of graphite oxides. The graphite oxides were first prepared by Staudenmaier, Hofmann, and Hummers methods followed by treatments in hydrogen sulfide, sulfur dioxide, or carbon disulfide. The doped materials were characterized by scanning electron microscopy, high-resolution X-ray photoelectron spectroscopy, combustible elemental analysis, and Raman spectroscopy. The ζ-potential and conductivity of sulfur-doped graphenes were also investigated in this paper. It was found that the level of doping is more dramatically influenced by the type of graphite oxide used rather than the type of sulfur-containing gas used during exfoliation. Resulting sulfur-doped graphenes act as metal-free electrocatalysts for an oxygen reduction reaction.

Diaryl thioethers and S-cycles were obtained on the basis of the copper-catalyzed reaction of carbon disulfide and aryl iodides in the presence of DBU. This reaction enables the one-pot synthesis of diaryl thioethers by employing cheap, available, and easy-to-handle carbon disulfide with aryl iodides. The reaction was successfully employed in the construction of sulfur-containing cyclic molecules.

The bimetallic aluminum(salen) complex [Al(salen)]2O is shown to catalyze the synthesis of oxazolidinones from epoxides and isocyanates. The reaction is demonstrated to proceed with overall retention of epoxide stereochemistry, and both aromatic and aliphatic isocyanates can be used as substrates. In contrast to the corresponding reactions between epoxides and carbon dioxide or carbon disulfide which are also catalyzed by [Al(salen)]2O, no cocatalyst is needed in the reactions with isocyanates. A mechanism is proposed which involves breaking and reforming of the Al–O–Al unit during the catalytic cycle, and this is supported by results obtained using monometallic catalysts.