Zur Reaktion von Carben-Addukten des Kohlenstoffdisulfids mit Brom und Iod [1] / On the Reaction of Carbene Adducts of Carbon Disulfide with Bromine and Iodine [1]

Kühn, Norbert; Bohnen, Hans; Henkel, Gerald

doi:10.1515/znb-1994-1105

Cited by 88 publications

(52 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…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: 46%

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

View full text Add to dashboard Cite

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.

show abstract

Section: Interpretation and Discussionmentioning

confidence: 46%

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

View full text Add to dashboard Cite

show abstract

“…When a larger proportion of halogen is employed, only uncharacterized decomposition products are obtained, probably due to halogenation of the alkyl side-chains. [34] ( 14) A different reaction path is observed with iodine. In this case, addition of a stoichiometric amount of halogen affords the intermediate charge-transfer complex 5, whose molecular structure has been established by XRD.…”

Section: Reactivitymentioning

confidence: 96%

“…A first report focused on the preparation and characterization of three adducts bearing simple alkyl groups on their nitrogen atoms (R = Me, Et, iPr). [34] The authors later complemented this study by introducing alkoxy-terminated alkyl chains at the heterocycle 1,3-positions [R = (CH 2 ) 2 OMe or (CH 2 ) 3 OMe]. [35] Their methodology was further exploited by Enders and co-workers in 1996 to prepare the CS 2 adduct of 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene [Equation (8)].…”

Section: Synthesismentioning

confidence: 99%

See 1 more Smart Citation

Betaine Adducts of N‐Heterocyclic Carbenes: Synthesis, Properties, and Reactivity

2009

View full text Add to dashboard Cite

N‐Heterocyclic carbenes (NHCs) form stable zwitterionicadducts with a range of heteroallenes, ketenes, and allenes. Although the first representatives of this class of inner salts were first investigated as far back as the 1960s, they have enjoyed a sustained interest from the chemical community over the years. Depending on the nature of their anionic moiety, NHC betaines display a very broad palette of reactivities and have found applications in various fields of organic synthesis and catalysis. In this Microreview, the synthesis, properties, and reactivity of NHC betaines are surveyed. The NHCs under consideration include ylidenes derived from imidazole, benzimidazole, imidazoline, thiazole, or triazole, and the heteroallenes investigated so far are carbon dioxide, carbon disulfide, isocyanates, isothiocyanates, and their selenium analogues. A historical background is provided for each type of adduct under consideration, but emphasis is placed mainly on developments that have appeared in the literature within the past few years. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

show abstract

“…This approach was later supplemented by the addition of stable dihydroimidazol-2-ylidenes to CS 2 , 102 Ǟ 154. [213] A non-carbenic route (to 157), the sulfurization of enediamines 156, also dates back to 1965. [214] Improved procedures utilize the reactions of 156b,c with elemental sulfur, or of 156a with S 2 Cl 2 .…”

Section: Betainesmentioning

confidence: 99%

Carbene Complexes of Nonmetals

Kirmse

2005

Eur J Org Chem

View full text Add to dashboard Cite

Electrophilic carbenes accept a variety of n‐ and π‐donors. The products range from persistent ylides to matrix‐isolated xenon complexes. Ylides can be viewed as carbene complexes if they regenerate carbenes thermally or undergo concerted methylene transfer reactions. According to these definitions, the present review focuses on oxonium and iodonium ylides. Transient π‐complexes appear to be involved in addition reactions of carbenes with arenes (but not with alkenes). Nucleophilic carbenes form adducts with Lewis acids which are, for the most part, stable and have been well characterized structurally. Only recently attention has been directed to reversible systems. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

show abstract

Zur Reaktion von Carben-Addukten des Kohlenstoffdisulfids mit Brom und Iod [1] / On the Reaction of Carbene Adducts of Carbon Disulfide with Bromine and Iodine [1]

Cited by 88 publications

References 4 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

Betaine Adducts of N‐Heterocyclic Carbenes: Synthesis, Properties, and Reactivity

Carbene Complexes of Nonmetals

Contact Info

Product

Resources

About