Gas-phase specific reactivity of isomeric 1,3-benzodithiole anions: Tandem mass spectrometry and DFT theoretical studies

Gimbert, Y;Arnaud, R;de Hoffman, E;Tabet, JC
(2001) The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory — Vol. 105, n° 21, p. 5221-5231 (2001)

Files

pdfdocument.pdf
  • Restricted Access
  • Adobe PDF
  • 371.71 KB
No access

Details

Authors
  • Gimbert, Y
    Author
  • Arnaud, R
    Author
  • de Hoffman, E
    Author
  • Tabet, JC
    Author
Abstract
1,3-Benzodithiole dideuterated at the dithioacetal carbon atom has been ionized in the chemical ionization source of a tandem triple quadrupole mass spectrometer under NICI condition. Two isomeric anions are formed by abstraction of an o-phenylic proton or through abstraction of a deuteron. The fragmentation patterns occurring under dissociative collisions differ and confirm the coexistence of two nonconverting carbanions. DFT calculations show that the dithioacetal anion is more stable than the phenylic. The nucleophilic reactivity toward CS2 has been studied by collision-induced reactions in the collision cell of the tandem instrument. Both isomeric anion forms display characteristic fragmentations of the resulting [(M-H(D)) + CS2] adduct anions, demonstrating a difference in reactivity: the dithioacetal anion reacts regioselectively at C and the o-phenylic at S, DFT calculations, performed with the aim of rationalizing this observed difference and understanding the formation of the diagnostic fragments, have been successful.
Affiliations

Citations

  • APA
  • Chicago
  • FWB

Gimbert, Y., Arnaud, R., de Hoffman, E., & Tabet, J. (2001). Gas-phase specific reactivity of isomeric 1,3-benzodithiole anions: Tandem mass spectrometry and DFT theoretical studies. The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 105(21), 5221-5231. https://doi.org/10.1021/jp003294j (Original work published 2001)