Spectroscopic identification of 2,5-dimercapto-1,3,4-thiadiazole and its lithium salt and dimer forms

Pope, John M.; Sato, Tomotaka; Shoji, Eiichi; Buttry, Daniel A.; Sotomura, Tadashi; Oyama, Noboru

doi:10.1016/s0378-7753(96)02598-0

Cited by 30 publications

(27 citation statements)

References 18 publications

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“…6,47 While interest in this area has been directed toward characterizing the redox behavior of DMcT in dilute nonaqueous solutions, the complexity of its spectra and the inconsistencies between previous studies have prompted us to investigate first the structure of DMcT and derivatives in the solid phase. ͑Preliminary assignment of the vibrational bands of DMcT and a few derivatives has been reported, 48 this contribution represents our complete efforts in that context.͒ In the first part of this report, the experimentally observed vibrational bands are assigned to their primary contributing bonds through the combined use of systematic chemical derivatization of DMcT, and deuteration of certain derivatives, correlated with a survey of published results. Specifically, we have performed Fourier transform nuclear magnetic resonance ͑NMR͒ cross-polarization magic angle spinning ͑CPMAS͒, infrared Fourier transform infrared ͑FTIR͒, and Raman spectroscopic studies of solid samples of DMcT, the lithium salts of its two conjugate base forms, its dimer and polymer forms, and two methyl derivatives.…”

mentioning

confidence: 81%

Organosulfur/Conducting Polymer Composite Cathodes

Pope¹,

Sato²,

Shoji³

et al. 2002

J. Electrochem. Soc.

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The dimercaptan 2,5-dimercapto-1,3,4-thiadiazole ͑DMcT͒ has been employed as a component in secondary lithium battery cathodes. However, spectroscopic studies of its behavior have been impeded by general uncertainty regarding its vibrational band character. The purpose of this study is to provide a spectroscopic basis for the unambiguous determination of protonation and oxidation state of DMcT. The first part of this paper is concerned with structural and spectroscopic assignment of DMcT and some derivatives. Several structural and spectroscopic assignments are intrinsically interesting, including ͑i͒ the suggestion that the thioamide-containing compounds adopt the thione tautomer structure whenever the opposite nitrogen is unsubstituted and ͑ii͒ assignment of an A 1 ring mode for the first time for these compounds. The second part of this paper uses that resource to examine the in situ Raman spectroelectrochemistry of DMcT in a nonaqueous solvent. The results confirm, in part, the redox wave assignments made previously in the literature. Specifically, Raman spectroelectrochemistry of solutions of DMcT and the lithium salt of its first conjugate base ͑LiDMcT͒ show that at ca. 0.8 V LiDMcT is oxidized while DMcT is not oxidized, and that at ϩ1.9 V both species were oxidized. Results regarding oxidation-initiated precipitation of oligomers are also reported.

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confidence: 81%

Organosulfur/Conducting Polymer Composite Cathodes

Pope¹,

Sato²,

Shoji³

et al. 2002

J. Electrochem. Soc.

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“…943, 670 and 513 cm À1 are weak, they are characteristic because they do not appear in the FTIR spectra of either the pyrolysate of PAN or elemental sulfur. The peak at 513 cm À1 can be ascribed to the S-S stretching, based on assignments for organodisulfides [4,24]. Because elemental sulfur is inactive in IR, the vibration at 513 cm À1 can be caused only by stretching of S-S bonds in the compound-state.…”

Section: Materials Characterizationmentioning

confidence: 99%

Lithium storage in conductive sulfur-containing polymers

Xie

Yang

et al. 2004

Journal of Electroanalytical Chemistry

102

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“…Figure 7a shows the SERS spectrum of DMTD adsorbed on the copper surface immediately after withdrawing of the sample from DMTD solution. The strong band at 1376 cm -1 indicates that the reaction product of DMTD with metallic copper surface is a disulfide salt of DMTD, 49 although the IR spectrum of Cu-I indicates a monosulfide salt of DMTD. Thus, a transition state must exist between the above two products during the surface reaction.…”

Section: Surface Reactions Of Dmtd With Zero Oxidationmentioning

confidence: 99%

Chemical Reactions of 2,5-Dimercapto-1,3,4-thiadiazole (DMTD) with Metallic Copper, Silver, and Mercury

Huang

Tang

et al. 2001

J. Phys. Chem. B

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Chemical reactions of DMTD with metallic copper, silver, and mercury have been studied by infrared (IR), surface-enhanced Raman scattering (SERS), UV-vis, and X-ray photoelectron spectrum (XPS) techniques. It is found that DMTD can react readily with metallic copper, silver, and mercury under mild conditions. The reaction product of DMTD with metallic copper shows an IR spectrum slightly different from that of Cu-(DMTD) 2 , suggesting a Cu + component in the product, which is further confirmed by the XPS result. The reaction products of DMTD with metallic silver and liquid mercury are Ag(DMTD) and Hg(DMTD) 2 , respectively. A two-step mechanism is proposed for these surface reactions: first DMTD is chemisorbed on the metal surfaces with the formation of the disulfide salt of DMTD as the intermediate product, and then the unstable disulfide salt reacts further with the excessive DMTD in solution, forming the monosulfide salt of DMTD which covers the metal surfaces in the form of a polymer layer or even a monolayer.

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Spectroscopic identification of 2,5-dimercapto-1,3,4-thiadiazole and its lithium salt and dimer forms

Cited by 30 publications

References 18 publications

Organosulfur/Conducting Polymer Composite Cathodes

Organosulfur/Conducting Polymer Composite Cathodes

Lithium storage in conductive sulfur-containing polymers

Chemical Reactions of 2,5-Dimercapto-1,3,4-thiadiazole (DMTD) with Metallic Copper, Silver, and Mercury

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