Formation of stable aryldisulphide ions in dimethylacetamide from the reaction of sulphur with thiolate ions

Benaichouche, M.; Bosser, G.; Paris, Jacky; Auger, J.; Plichon, V.

doi:10.1039/p29900000031

Cited by 18 publications

(29 citation statements)

References 27 publications

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“…19,20 The diorganyl disulphides are capable of undergoing electrochemical reduction to thiolate ions (RS -) in aprotic media and the previously reported reduction potential for Ph2S2 is ~2.08 V (vs. Li/Li + ). 21,22 The single step reduction process to form thiolate ions is of other anions such as cyanides (CN-), sulphites (SO3 2-) or arsenites (AsO3 3-) to form thiocyanides (SCN -), thiosulphates (S2O3 2-) or shown in equation ( 4) in Scheme 1. These thiolate anions have an affinity for sulphur atoms which has been termed as 'Snucleophilicity' or 'thiophilicity' by Kharasch and Parker.…”

Section: -Results and Discussionmentioning

confidence: 99%

Catholyte Formulations for High-Energy Li–S Batteries

Phadke

Coadou

Anouti

2017

J. Phys. Chem. Lett.

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The sulfur electrode in LiS batteries suffers from rapid capacity loss and low efficiency due to the solubility of long chain polysulfides formed during discharge. Herein, we demonstrate the beneficial effect of original catholyte formulations containing redox active organyl disulfides (PhSPh) on the capacity utilization and retention as well as the efficiency in LiS batteries. Resulting from the chemical equilibria in the electrolyte between the sulfur/polysulfides (S/S) and disulfide/thiolates (PhSPh/PhS), the polysulfide redox shuttle phenomenon is minimized due to the suppression of formation of soluble polysulfides (S, x > 4). Using the catholyte containing 0.4 M PhS as an additive in a standard base electrolyte (DOL/DME + LiTFSI/LiNO), a stable capacity of 1050 mAh·g is obtained under galvanostatic cycling at C/5 with a Coulombic efficiency of >99.5%. At 45 °C, it is shown that the formulated catholyte enables galvanostatic cycling at a high c-rate of 1C over 500 cycles with a capacity above 900 mAh·g and a high energy efficiency of 82%.

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Section: -Results and Discussionmentioning

confidence: 99%

Catholyte Formulations for High-Energy Li–S Batteries

Phadke

Coadou

Anouti

2017

J. Phys. Chem. Lett.

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“…It is known from the literature that this kind of molecules forms complex equilibria in solution. 1,2,7 The intense blue-Fig. 6: Crystal structure (50% probability ellipsoids) of the oxidation product of 1b (4).…”

Section: Dynamics In Solutionmentioning

confidence: 99%

“…to-green color at r.t. can be explained by the presence of the strongly colored S3 .radical that is formed together with diphenyl disulfide by the reactions shown in Scheme 2Scheme 2. 1,2,7 This process, however, only happens to a very limited extent. The 1 H-NMR spectra in MeCN-d3…”

Section: Dynamics In Solutionmentioning

confidence: 99%

“…They have only been observed and investigated in dimethylacetamide (DMA) solutions. 1,2,[4][5][6] The single exception was prepared as a metal-containing 2:1 salt [M (Nmethylimidazole)6](PhS2)2 for M = Mn and Ni. 7 Given the paucity of experimental data and the lack of accessible pure compounds of this kind, it is no surprise that the fundamental chemistry of the monoorganylpolysulfanide species is still poorly understood.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Spectroscopic, and Structural Characterization of Organyl Disulfanides and a Tetrasulfanide

2020

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Various room-temperature-stable monoorganylpolysulfanides of the form X + RSn -(n ≥ 2) were synthesized in a simple and versatile one-step process starting from sodium thiolates and elemental sulfur. The compounds were characterized by X-ray crystal structure analysis, NMR spectroscopy, microelemental analysis and electrospray mass ionization spectrometry including collision-induced dissociation experiments. While these salts are well-defined species as crystals, they undergo complex equilibria in solution. In one case, compounds ranging from n = 1-8 have been observed in solution. Structural features, dynamics in solution as well as thermochromic properties of one of the compounds, PPh4 + PhS2 -, are investigated in detail by temperature-and pressure-dependent X-ray crystal structure analysis. The experimental data is complemented by periodic boundary density functional theory calculations on the crystal structures, as well as energy decomposition analyses.

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“…This electrochemical behavior is in agreement with previously reported results and it is similar to the one proposed for the reduction of some aromatic disulfides. 35,36,54,55 One may also observe from Figure 5 that the electrochemical response of pyritinol in CNF-GNP/SPCE is considerably improved in terms of both peak current and peak shape, compared to that in case of CNF/SPCE and SPCE. This suggests that the oxidation of pyritinol is more favorable on the surface of CNF-GNP/SPCE than on other two electrodes used.…”

Section: Results and Discussion Electrochemical Properties Of Cnf-gnpmentioning

confidence: 76%

Highly sensitive voltamperometric determination of pyritinol using carbon nanofiber/gold nanoparticle composite screen-printed carbon electrode

Apetrei¹,

Apetrei

2017

IJN

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A novel and highly sensitive electrochemical method for the detection of pyritinol in pharmaceutical products and serum samples has been accomplished based on voltamperometric response of pyritinol in carbon nanofiber-gold nanoparticle (CNF-GNP)-modified screen-printed carbon electrode (SPCE). The electrochemical response of pyritinol to CNF-GNP-modified SPCE was studied by cyclic voltammetry and square-wave voltammetry (SWV). Under optimized working conditions, the novel sensor shows excellent voltamperometric response toward pyritinol. The SWV study shows significantly enhanced electrochemical response for pyritinol in CNF-GNP-modified SPCE providing high sensitivity to the novel sensor for pyritinol detection. The peak current for pyritinol is found to be linear with the concentration in the range 1.0×10 −8 –5.0×10 −5 M with a detection limit of 6.23×10 −9 M using SWV as the detection method. The viability of the new developed sensor for the analytical purposes was studied by performing experiments on various commercial pharmaceutical products and blood serum samples, which yielded adequate recoveries of pyritinol. The novel electrochemical sensor provides high sensitivity, enhanced selectivity, good reproducibility and practical applicability.

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Formation of stable aryldisulphide ions in dimethylacetamide from the reaction of sulphur with thiolate ions

Cited by 18 publications

References 27 publications

Catholyte Formulations for High-Energy Li–S Batteries

Catholyte Formulations for High-Energy Li–S Batteries

Synthesis, Spectroscopic, and Structural Characterization of Organyl Disulfanides and a Tetrasulfanide

Highly sensitive voltamperometric determination of pyritinol using carbon nanofiber/gold nanoparticle composite screen-printed carbon electrode

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