3,6-Dihydro[1,2]dithiolo[4,3-c][1,2]dithiole-3,6-dithione and oxo analogues: a comparative study of the thermal (FVP) and electron ionization (EI) induced fragmentations

Pedersen, C. Th.; Flammang, Robert; Gerbaux, Pascal; Fanghänel, E.

doi:10.1039/a800654g

Cited by 7 publications

(4 citation statements)

References 22 publications

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“…This observation is in line with the reported ability of the b,b-C 4 S 6 isomer 1 to act as a source for carbon subsulfide C 3 S 2 under flash vacuum pyrolysis conditions. 24 Both 1 and 4 contain in the molecule a SCCCS moiety whereas this moiety is not present in the structure of 3 and accordingly no fragmentation to C 3 S 2 is observed in its mass spectrum. Compound 4 can thus also be expected to be a source for the synthesis of carbon subsulfide C 3 S 2 under flash vacuum pyrolysis conditions.…”

Section: Resultsmentioning

confidence: 98%

Isomers among the carbon sulfides C₄S₆—synthesis and crystal structures of α,α-C₄S₆, α,β-C₄S₆, and of a second polymorph of the diiodine adduct α,β-C₄S₆·I₂

et al. 2006

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The reaction of the alpha and beta forms of C3S5(2-) with thiophosgene yields two isomeric carbon sulfides alpha,alpha-C4S6 and alpha,beta-C4S6, respectively. The crystal structures of both compounds could be determined for the first time. Both structures are made up of almost planar molecules. The alpha,alpha-isomer (1,3-dithiolo-(4,5-d)-1,3-dithol-2,5-dithione) is D2h-symmetric, while the alpha,beta-isomer is approximately Cs-symmetric. In the molecules of both isomers the two different C3S5 units are retained without significant alterations of structural parameters. alpha,alpha-C4S6 is unstable with respect to alpha,beta-C4S6. The molecular rearrangement can be induced by a short thermal treatment at 150 degrees C. Significant differences are found in the mass spectra fragmentation patterns. Only alpha,beta-C4S6 shows an intense signal for C3S2+ and is therefore a potential source for the synthesis of carbon subsulfide via flash vacuum pyrolysis. Only alpha,beta-C4S6 forms a stable adduct with I2. alpha,beta-C4S6.I2 was already known (F. L. Lu, K. M. Keshavarz-K, G. Srdanov, R. H. Jacobson and F. Wudl, J. Org. Chem., 1989, 54, 2165, ), but a second polymorph is formed on crystallisation from a different solvent. The two polymorphic forms do not show differences in the structures of the individual molecules but show a different packing pattern. alpha,beta-C4S6.I2 is remarkably thermally stable. Thermal analysis shows that I2 cleavage occurs in that temperature region above 200 degrees C when C-S bonds are broken and CS2 and I2 are simultaneously liberated. Performed at 270 degrees C thermolysis of alpha,beta-C4S6.I2 yields under cleavage of I2 and CS2 a black polymeric carbon sulfide (CS)x which is probably a mixture of graphitic carbon and unidentified amorphous polymeric carbon sulfides.

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Section: Resultsmentioning

confidence: 98%

Isomers among the carbon sulfides C₄S₆—synthesis and crystal structures of α,α-C₄S₆, α,β-C₄S₆, and of a second polymorph of the diiodine adduct α,β-C₄S₆·I₂

et al. 2006

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“…In contrast to the OCCCSS •+ and SCCCSS •+ ions which react specifically with nitric oxide producing SNO + ( m / z 62) ions, the behavior of the m / z 120 ions of 1 is completely unexpected and appears quite complex, as prominent peaks are now seen at m / z 106, 88, 86, 76, and 74 (among these ions, m / z 88 and 76 ions are the products of unimolecular fragmentation of metastable m / z 120 ions); formation of SNO + ions is a minor process (Figure a). Given the composition of the reacting ions and the nature of the reagent gas, the composition of the ion−molecule products must be CNOS 2 , C 2 NOS, and CNOS, respectively.…”

Section: Mass Spectrometric Resultsmentioning

confidence: 67%

“…The behavior of the m / z 120 ions derived from 2 appears to be intermediate between 1 and 3 , again in agreement with the production of a mixture of isomers in different proportions (Figure b). It is worthy to note that CS 3 •+ ions or the cumulogue C 3 S 3 •+ ions react also with nitric oxide in the quadrupole collision cell, but the major product ion is in these cases ONS + ( m / z 62). , It is proposed that the reactive species are in these cases SCSS •+ and SCCCSS •+ ions, respectively, with the losses of the stable SCS or reasonably stable SCCCS cumulenes. The same reaction for the SCCSS •+ should be the loss of ethenedithione, SCCS, a less stable cumulene having an even number of carbon atoms.…”

Section: Mass Spectrometric Resultsmentioning

confidence: 99%

“…During the study of the behavior of dithiolodithioles upon flash vacuum pyrolysis (FVP) making use of matrix isolation infrared spectroscopy and tandem mass spectrometry, it was noticed that, following dissociative electron ionization of 1 and 2 , unexpected ion species were generated at m / z 116 for 1 and m / z 132 for 2 . High-resolution mass measurements have confirmed the composition of these species as C 3 OS 2 and C 3 S 3 , respectively and applications of tandem mass spectrometric methodologies have supported the OCCCSS and SCCCSS connectivities (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

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Characterization of New Sulfide Ions (C₂S₃^•+) from Ethenedithione by Ion−Molecule Reactions

Gerbaux

Flammang

Pedersen³

et al. 1999

J. Phys. Chem. A

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Collisional activation (high or low translational energy) and neutralization-reionization mass spectrometries appear inefficient for the characterization of the connectivity of isomeric C 2 S 3 •+ ions generated by dissociative ionization of 1,2-dithiolo[4,3-c][1,2]dithiole-3,6-dione (1), 1,2-dithiolo[4,3-c][1,2]dithiole-3-one-6-thione (2), and 1,3,4,6-tetrapentalene-2,5-dione (3). In contrast, ion-molecule reactions (particularly with nitric oxide) readily differentiate the C-sulfide ethenedithione ion, SCCS 2 •+ (4), and the S-sulfide ethenedithione ion, SCCSS •+ (5). The collisional activation spectra of these ion-molecule reaction products have been recorded on a new type of hybrid tandem mass spectrometer of sectors-quadrupole-sectors configuration. The characterization of the isomeric C 2 S 3 •+ ions is supported by ab initio calculations at the G2(MP2,SVP) level. The C-sulfide ethenedithione ion is predicted to be more stable than the S-sulfide form by 91 kJ mol -1 . The calculated reaction enthalpies for the two isomeric forms C 2 S 3 •+ with nitric oxide support the characterization by ion-molecule reactions. IntroductionDuring the study of the behavior of dithiolodithioles upon flash vacuum pyrolysis (FVP) making use of matrix isolation infrared spectroscopy and tandem mass spectrometry, 1 it was noticed that, following dissociative electron ionization of 1 and 2, unexpected ion species were generated at m/z 116 for 1 and m/z 132 for 2. High-resolution mass measurements have confirmed the composition of these species as C 3 OS 2 and C 3 S 3 , respectively and applications of tandem mass spectrometric methodologies have supported the OCCCSS and SCCCSS connectivities (Scheme 1).Carbon monoxide is indeed readily expelled from the molecular ions of the dithiolodithioles 1 and 2 and, in a consecutive reaction, the intermediate radical cations eliminate disulfur. Another competitive reaction consists of the loss of carbon disulfide or carbon oxysulfide producing C 2 S 3 •+ radical cations (m/z 120). If the mechanisms depicted in Scheme 1 are correct, one may expect the formation of ethenedithione S-sulfide ions, SdCdCdS + -S • (5). In fact, the isomeric dithiolodithiole 3 is also an excellent precursor of C 2 S 3 •+ radical cations, 2 and given the arrangement of the atoms in the neutral precursor, one would expect that its dissociative ionization could produce the isomeric C-sulfurated species, SdCdCS 2 •+ (4).In connection with our current interest with the chemistry of C n S 3 •+ radical cations, 3 we have therefore applied tandem mass spectrometry methodologies to the C 2 S 3 •+ radical cations (m/z 120) making use of a new type of hybrid mass spectrometer. 4,5 The performed MS experiments include collisional activation (CA) at high (8 keV) and low (ca. 20-30 eV) translational energies of the incident ion beams, neutralization-reionization

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Characterization of C2S4·+ isomers by mass spectrometry and ab initio molecular orbital calculations

Gerbauxa¹,

Flammanga²,

Wentrup³

et al. 2001

International Journal of Mass Spectrometry

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3,6-Dihydro[1,2]dithiolo[4,3-c][1,2]dithiole-3,6-dithione and oxo analogues: a comparative study of the thermal (FVP) and electron ionization (EI) induced fragmentations

Cited by 7 publications

References 22 publications

Isomers among the carbon sulfides C₄S₆—synthesis and crystal structures of α,α-C₄S₆, α,β-C₄S₆, and of a second polymorph of the diiodine adduct α,β-C₄S₆·I₂

Isomers among the carbon sulfides C₄S₆—synthesis and crystal structures of α,α-C₄S₆, α,β-C₄S₆, and of a second polymorph of the diiodine adduct α,β-C₄S₆·I₂

Characterization of New Sulfide Ions (C₂S₃^•+) from Ethenedithione by Ion−Molecule Reactions

Characterization of C2S4·+ isomers by mass spectrometry and ab initio molecular orbital calculations

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3,6-Dihydro[1,2]dithiolo[4,3-c][1,2]dithiole-3,6-dithione and oxo analogues: a comparative study of the thermal (FVP) and electron ionization (EI) induced fragmentations

Cited by 7 publications

References 22 publications

Isomers among the carbon sulfides C4S6—synthesis and crystal structures of α,α-C4S6, α,β-C4S6, and of a second polymorph of the diiodine adduct α,β-C4S6·I2

Isomers among the carbon sulfides C4S6—synthesis and crystal structures of α,α-C4S6, α,β-C4S6, and of a second polymorph of the diiodine adduct α,β-C4S6·I2

Characterization of New Sulfide Ions (C2S3•+) from Ethenedithione by Ion−Molecule Reactions

Characterization of C2S4·+ isomers by mass spectrometry and ab initio molecular orbital calculations

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Isomers among the carbon sulfides C₄S₆—synthesis and crystal structures of α,α-C₄S₆, α,β-C₄S₆, and of a second polymorph of the diiodine adduct α,β-C₄S₆·I₂

Isomers among the carbon sulfides C₄S₆—synthesis and crystal structures of α,α-C₄S₆, α,β-C₄S₆, and of a second polymorph of the diiodine adduct α,β-C₄S₆·I₂

Characterization of New Sulfide Ions (C₂S₃^•+) from Ethenedithione by Ion−Molecule Reactions