Zwitterionic dithiocarboxylates derived from N-heterocyclic carbenes: coordination to gold surfaces

Siemeling, Ulrich; Memczak, Henry; Bruhn, Clemens; Vogel, Florian; Träger, F.; Baio, Joe E.; Weidner, Tobias

doi:10.1039/c2dt11976e

Cited by 41 publications

(38 citation statements)

References 69 publications

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“…In previous study, these transitions have been tentatively assigned to the presence of traces of 1-butyl-3-methylimidazolium-2-dithiocarboxylate [Bmim] CS 2 although the resonance line of the carbon atom of the dithiocarboxylate ∼220-225 ppm was not detected by NMR. 4,28,31 Therefore, it can be inferred from the present results that it is the trithiocarbonate anion which has been formed and not the dithiocarboxylate. Although the formation of the latter species cannot be totally ruled out, the present analysis shows that if formed it suffered such degradation in a short time scale (typically less than 15 min) that it could not be observed experimentally.…”

Section: Interpretation and Discussionmentioning

confidence: 80%

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Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Cabaço¹,

Besnard

Chávez

et al. 2014

The Journal of Chemical Physics

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NMR spectroscopy ( 1 H, 13 C, 15 N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS 2 leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH 3 COS − ), CO 2 , OCS, and trithiocarbonate (CS 3 2− ). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro] + cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on (2), and CO 2 - [Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS 2 reacts with the acetate anion leading to the formation of CH 3 COS − , CO 2 , and OCS. After these reactions have proceeded the nascent CO 2 and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO 2 ) and imidazoliumthiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO 2 - [Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO 2 molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO 2 , whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim] CS 2 is unfavoured and that the anion offers a competitive reactive channel via an oxygensulphur exchange mechanism with the solute in systems (1) and (2). © 2014 AIP Publishing LLC.

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Section: Interpretation and Discussionmentioning

confidence: 80%

“…6). The blood-red color of this solution and the observation in UV-Visible spectroscopy of two n → π * transitions of sulfur 27,31,39,[43][44][45] close to those found in the CS 2 -[BmPyrro]…”

Section: Interpretation and Discussionmentioning

confidence: 99%

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Cabaço¹,

Besnard

Chávez

et al. 2014

The Journal of Chemical Physics

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“…In previously reported imidazolium-2-dithiocarboxylates the CS 2 carbon resonance is usually observed in the range 220 -226 ppm, and the C 2 in the unsaturated imidazolium ring around 149 ppm. 30,31 In a separate reaction, we also isolated the CS 2 adduct of the proligand, HL.CS 2 ; full characterisation including a single crystal X-ray structure, is in the SI. * Crystals of 4 were also grown by adding a few drops of thf, then three equivalents of CS2 to a toluene solution of 1 at room temperature.…”

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confidence: 99%

Activation of carbon dioxide and carbon disulfide by a scandium N-heterocyclic carbene complex

et al. 2014

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“…The mean C-C bond distance between the N 2 C + unit and the CS 2 − unit in 4 is 1.481 Å. 5,31,32 Most surprising in both 3 and 4 is the absence of interaction between the scandium centre and the CS 2 group, despite its formal negative charge. 9 To conclude, Sc(L) 3 readily incorporates three equivalents of CO 2 showing 'Frustrated Lewis Pair' type reactivity, but it has not been possible to incorporate fewer equivalents.…”

mentioning

confidence: 97%

“…In previously reported imidazolium-2-dithiocarboxylates the CS 2 carbon resonance is usually observed in the range 220-226 ppm, and the C 2 in the unsaturated imidazolium ring around 149 ppm. 30,31 In a separate reaction, we also isolated the CS 2 adduct of the proligand, HL·CS 2 ; full characterisation including a single crystal X-ray structure, is in the ESI. † Treatment of 1 with two equivalents of CS 2 in toluene leads to immediate formation of 3, followed by the slow formation of [Sc(OCMe 2 CH 2 (1-S 2 CC{NCHCHN i Pr})) 2 (L)], 4 abbreviated as Sc(L CS2 ) 2 (L), as a red oil, evidenced by monitoring the reaction by 1 H NMR.…”

mentioning

confidence: 99%

Self-Assembly Fabrication of Hollow Mesoporous Silica@Co–Al Layered Double Hydroxide@Graphene and Application in Toxic Effluents Elimination

Jiang

Song

Zeng

et al. 2015

ACS Appl. Mater. Interfaces

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Here, we propose a self-assembly process to prepare hierarchical HM-SiO2@Co–Al LDH@graphene, with the purpose of combining their outstanding performance. Hollow mesoporous silica was first synthesized as the core, using a novel sonochemical method, followed by a controlled shell coating process and chemical reduction. As a result of the electrostatic potential difference among HM-SiO2, Co–Al LDH, and graphene oxide, the HM-SiO2 spheres were coated by Co–Al LDH and graphene. Subsequently, the HM-SiO2@Co–Al LDH@graphene spheres were introduced into an epoxy resin (EP) matrix for investigation of their toxic effluents capture and elimination effectiveness during combustion. The amount of toxic CO and volatile organic compounds from the epoxy resin decomposition significantly suppressed after incorporating the HM-SiO2@Co–Al LDH@graphene hybrids, implying a reduced toxicity.

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Zwitterionic dithiocarboxylates derived from N-heterocyclic carbenes: coordination to gold surfaces

Cited by 41 publications

References 69 publications

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Activation of carbon dioxide and carbon disulfide by a scandium N-heterocyclic carbene complex

Self-Assembly Fabrication of Hollow Mesoporous Silica@Co–Al Layered Double Hydroxide@Graphene and Application in Toxic Effluents Elimination

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