Thermal stability of dialkyldithiocarbamates

Afanasova, G.P.; Shkhiyants, I. V.; Nechitailo, N. A.; Sher, V. V.; Sanin, P.I.

doi:10.1016/0031-6458(71)90016-5

Cited by 2 publications

(3 citation statements)

References 4 publications

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“…Most of the ti'agmentation processes were metastable supported. For example, in the case of the complex [Fe(S2CNEt2)2C1]2(#-I2) the existence of metastable peaks at m* = 118.2, m* = 62.9, and m* = 34.6 confirms the following fragmentations: [18][19][20] for several metal dithiocarbamate complexes. Considering the above results, it becomes evident that the fragmentation patterns derived from the mass spectral study of the investigated compounds are in good agreement with the thermal decomposition results.…”

Section: Apparent Activation Energy (E* )mentioning

confidence: 55%

“…The latter is probably due to the cleavage of one Fe---S bond and the loss of a dithiocarbamate radical. However, we might expect a low relative abundance of these ions, considering the known thermal instability of similar compounds [18,19] and organometallic compounds in general. A number of daughter ions, besides the ones mentioned above, were also detected.…”

Section: Apparent Activation Energy (E* )mentioning

confidence: 96%

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Thermal decomposition of some homobinuclear dihalide-bridged iron(III) complexes

Lalia‐Kantouri

Katsoulos

Vakoulis

1986

Journal of Thermal Analysis

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Thermal studies by TG and DTG on some homobinuclear dihalide-bridged iron(Ill) complexes of the general type [Fe(S2CNR2)2X]2~-X~) were carried out in air and nitrogen atmospheres. The apparent activation energies were determined by graphical methods and the TTN temperatures were calculated from the TG profiles. Finally, a possible mechanism of the decomposition is suggested on the basis of the pyrolysis and mass spectral data.In previous papers, results have been reported on the reactions of molecular halogens (X~) with the square-pyramidal complexes [Fe(S2CNR2)2X] (X = CI, Br, I) [1][2][3]. The salient feature of these reactions is the effect of the alkyl substituent in the dithiocarbamato ligand on the composition of the products obtained [4,5]. In this respect, a general mechanism accounting for the variety of products formed has been proposed [3].In this paper, we focus our attention on the binuclear iron(Ill) complexes formulated [2] as [Fe(S2CNR2)2X]2(/~-X~), where R = Me, Et, pri; X' = Br, I. M6ssbauer and magnetic measurements on this very interesting class of compounds, as well as an X-ray crystal structure determination [6] of another derivative of this series containing the pyrrolidinyldithiocarbamato ligand, have established the presence of the molecular halogen in the form of a bridging unit mediating the formation of weakly coupled dimers with antiferromagnetic interaction. In particular, the molecular halogen interacts weakly in an end-on fashion with the halide ligand of the mononuclear complexes, forming an extended tetratomic bridging unit, {X-X'-X'-X} 2-, between the two paramagnetic centres. Consequently, the binuclear complexes have been proved [7] to be potential carriers of activated molecular halogens and therefore very reactive in halogentransfer reactions.As an extension of our previous work [8][9][10] on thermal studies of metal diothiocarbamate complexes, a thermal investigation of the dihalide-bridged

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Section: Apparent Activation Energy (E* )mentioning

confidence: 55%

Section: Apparent Activation Energy (E* )mentioning

confidence: 96%

Thermal decomposition of some homobinuclear dihalide-bridged iron(III) complexes

Lalia‐Kantouri

Katsoulos

Vakoulis

1986

Journal of Thermal Analysis

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“…The absence of molecular ions can be attributed either to pyrolytic The highest mass number ions observed for all compounds, which might be direct fragments of the parent ion after the elimination of one halide ligand, are those of the general formulae [Fe(Rzdtc)X] § and [Fe(Rzdtc)X']*. We might expect low relative abundances of these ions considering the known thermal instability of similar compounds [15][16][17] Among the most interesting and prominent peaks detected in the high mass region of the spectra ofall the examined compounds are those corresponding to the ions [R2NC(: S)SSC(: S)NR2] +" and [R2NC(: S)SNRz] +. These ions may be partly considered to be pyrolytic products, because their relative intensities are affected by the temperature and the time spent in the direct inlet.…”

Section: Methodsmentioning

confidence: 95%

Mass spectral and thermogravimetric studies of some iron(III) binuclear complexes with bridging thiuram disulfide ligands

Katsoulos

Lalia‐Kantouri

Vakoulis

1986

Journal of Thermal Analysis

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Mass spectral and thermal studies by TG and DTG of some iron(Ill) binuclear complexes of the general type Fez(R2dte)2(tds')X~X~ have been carried out to determine their modes of decomposition. Fragmentation patterns are given and possible mechanisms are discussed.In addition to the variety of products formed [1][2][3][4] during the reaction of iron(Ill) halobisdithiocarbamates, [Fe(Rzdtc)2X ], with halogens, X' 2, some novel homobinuclear iron(Ill) complexes with two different coordination spheres around the magnetic centers have also been synthesized and studied [5], The formation of these products, formulated as Fe2(R2dtc)2(tds~ [R = Me; R 2 = Pyrr; X = CI, Br; and X' = Br, I], depends on the natures of both the molecular halogen and the reagent complex, as well as on the reaction conditions. In particular, the proposed mechanism [5] which accounts for the synthesis of these compounds involves as a first step the formation of the corresponding dihalide-bridged dimers, [Fe(R2dtc)zX]2(/I-X'2). Analogous iron(Ill) complexes have already been isolated and their structures were established on the basis of spectroscopic [1,3, 4] and X-ray crystal structure [6] determination methods, as well as the results of thermoanalytical studies [7]. Depending on the redox capacities of both the halogens and the dithiocarbamato ligands, an intramolecular electron transfer could take place resulting in the oxidation of half of the dithiocarbamate groups into thiuram disulfide. In this case. the dimeric compounds studied in the present paper are formed.Continuing our interest in the thermal investigation of metal dithiocarbamate complexes [7][8][9][10], we report in this paper results concerning mass spectral and thermogravimetric studies of complexes Fe2(R2dtc)z(tds~ The E* values for the main decomposition stage, derived from the Piloyan method [11], TTN calculations [12], and a proposed mechanism of the decomposition are also reported and discussed.

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Thermal stability of dialkyldithiocarbamates

Cited by 2 publications

References 4 publications

Thermal decomposition of some homobinuclear dihalide-bridged iron(III) complexes

Thermal decomposition of some homobinuclear dihalide-bridged iron(III) complexes

Mass spectral and thermogravimetric studies of some iron(III) binuclear complexes with bridging thiuram disulfide ligands

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