The Crystal Structure of Cesium Dimethyldithiocarbamate, CsS2CN(CH3)2.

Wahlberg, Anders; Nygren, Mats; Valde, Gunnar; Andresen, Arne F.; Sandström, M.

doi:10.3891/acta.chem.scand.30a-0433

Cited by 11 publications

(5 citation statements)

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“…It has been observed that the delocalization of the nitrogen electron pair into the dithiocarbamate group shortens the C−N bond length, because of the higher double-bond character, and modifies the infrared spectra of dithiocarbamates. − The barrier of internal rotation about the C−N bond is considerably higher in N , N -dialkylthioamides than in N , N -dialkylamides, due to the higher double-bond character of the C−N bond. − The rotation increases in dilute acid and is solvent dependent. , …”

Section: Discussionmentioning

confidence: 99%

Mechanisms of Acid Decomposition of Dithiocarbamates. 1. Alkyl Dithiocarbamates

et al. 1998

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The acid decomposition of some substituted methyldithiocarbamates was studied in water at 25 °C in the range of H o −5 and pH 5. The pH−rate profiles showed a bell-shaped curve from which were calculated the acid dissociation constants of the free and conjugate acid species and the specific acid catalysis rate constants k H. The Brønsted plot of k H vs pK N, the dissociation constant of the conjugate acid of the parent amine, suggests that the acid cleavage occurs through two mechanisms that depend on the pK N. The plot presents a convex upward curve with a maximum at pK N 9.2, which is consistent with the cleavage of the dithiocarbamate anion through a zwitterion intermediate and two transition states. For pK N < 9.2, the N-protonation is slower than the C−N bond breakdown. Inverse SIE showed that the zwitterion is formed through a late transition state. At pK N > 9.2, the C−N bond breakdown is the slowest step, and according to the inverse SIE, the transition state changes rapidly with the increase of pK N to a late transition state. The plot shows a minimum at pK N ∼10, indicating that a new mechanism emerges at higher values, and it is postulated that it represents a path of intramolecular S to N proton-transfer concerted with the C−N bond breakdown. The thiocarbonyl group acts as a powerful electron-withdrawing group, decreasing the basicity of the nitrogen of the parent amine by 14.1 pK units.

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Section: Discussionmentioning

confidence: 99%

Mechanisms of Acid Decomposition of Dithiocarbamates. 1. Alkyl Dithiocarbamates

et al. 1998

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“…The presence of a doublet in the C=S stretching region in both the ir and Raman spectra of bisdithiocarbamates is a good indication that the C=S bonds are different in the CS2-group, and this is confirmed by the structural results. Although the structures of many dithiocarbamates have been reported (18,19), the configuration of ethylenebisdithiocarbamate, especially in its alkali metal salt, is of particular interest as it may change upon complexation with metal ions. The present study reveals that the Hbisdtc anion is centrosymmetric and the two NCS,-groups are separated as much as possible, an expected conformation.…”

Section: Resultsmentioning

confidence: 99%

Spectroscopic and structural studies of some bisdithiocarbamates and cyclic thiones

Mak¹,

Jasim²,

Chieh³

1984

Can. J. Chem.

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. Can. J. Chcm. 62, 808 (1984). ' The syntheses of bisdithiocarbamates from diamines and CS, are described, and possible complications in these reactions explained. Ethylenebisdithiocarbamate was prepared from ethylenediamine and CS, in basic solution, but the same reaction using o-phenylenediamine led to a cyclization product, o-phenyleneimidazolidine-2-thione or benzimidazolidine-2-thione. In these reactions, if slightly insufficient amounts of CS2 are used, bisdithiocarbamates will not bc formed; instead, the cyclization reactions will occur, leading to the formation of thiones. Crystallographic studies were carried out for disodium ethylenebisdithiocarbamate and imidazolidine-2-thione or ethylenethiourea. The hexahydrate crystals of the former,

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“…The longest of these is in [Cs][S 2 CNMe 2 ] [30] and is just slightly shorter than the longest of the cesium-sulfur distances in 3. If all 11 cesium sulfur contacts in 3 are considered as bonding, then cesium is 11 coordinate.…”

Section: Resultsmentioning

confidence: 97%

“…The range of CsAS bond lengths quoted for the compounds, related to 3 and listed in Table 3, is 3.4555(5)-4.099(1) Å [30][31][32][33][34][35]. The longest of these is in [Cs][S 2 CNMe 2 ] [30] and is just slightly shorter than the longest of the cesium-sulfur distances in 3.…”

Section: Resultsmentioning

confidence: 99%