Structure, Stability, and Generation of CH3CNS

Melinda Krebsz; Balázs Hajgató; Gábor Bazsó; György Tarczay; Tibor Pasinszki

doi:10.1071/CH10303

RESEARCH FRONT

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Structure, Stability, and Generation of CH₃CNS

Melinda Krebsz ^A , Balázs Hajgató ^B , Gábor Bazsó ^A , György Tarczay ^A ^C and Tibor Pasinszki ^A ^C

+ Author Affiliations

- Author Affiliations

^A Institute of Chemistry, Eötvös Loránd University Budapest, PO Box 32,H-1518 Budapest 112, Hungary.

^B Department of Chemistry, Hasselt University, Research Group of Theoretical Chemistry and Molecular Modelling, Agoralaan, Gebouw D, B-3590 Diepenbeek, Belgium.

^C Corresponding authors. Email: pasinszki@chem.elte.hu; tarczay@chem.elte.hu

Australian Journal of Chemistry 63(12) 1686-1693 https://doi.org/10.1071/CH10303
Submitted: 13 August 2010 Accepted: 23 September 2010 Published: 6 December 2010

Abstract

The unstable acetonitrile N-sulfide molecule CH₃CNS has been photolytically generated in inert solid argon matrix from 3,4-dimethyl-1,2,5-thiadiazole by 254-nm UV irradiation, and studied by ultraviolet spectroscopy and mid-infrared spectroscopy. The molecule is stable in the matrix to 254-nm UV irradiation, but decomposes to CH₃CN and a sulfur atom when broad-band UV irradiation is used. Chemiluminescence due to S₂ formation from triplet sulfur atoms was detected on warming the matrix to ∼20–25 K. The ground-state structure and potential uni- and bimolecular reactions of CH₃CNS are investigated using B3LYP, CCSD(T), and MR-AQCC quantum-chemical methods. CH₃CNS is demonstrated to be stable under isolated conditions at room temperature, i.e. in the dilute gas phase or in an inert solid matrix, but unstable owing to bimolecular reactions, i.e. in the condensed phase.

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Structure, Stability, and Generation of CH3CNS

Abstract

References

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Structure, Stability, and Generation of CH₃CNS