Structure, Stability, and Generation of CH3CNS

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.

Generation and Spectroscopic Identification of Selenofulminic Acid and Its Methyl and Cyano Derivatives (XCNSe, X=H, CH3, NC)

“…A promising method for spectroscopic detection seems to be the generation of nitrile selenides in cold, inert noble gas matrices, in which thermal decomposition and bimolecular reactions are avoided. This is in line with the relevant nitrile sulfide chemistry, for which all of the four spectroscopically identified derivatives, HCNS, [9] FCNS, [10] CH 3 CNS, [11,12] and PhCNS, [12,13] have been identified at low temperatures and in inert matrices. Possible sources of nitrile selenides could be molecules containing the CNSe linkage and a good leaving group, releasing the desired product upon UV irradiation.…”

“…Possible sources of nitrile selenides could be molecules containing the CNSe linkage and a good leaving group, releasing the desired product upon UV irradiation. We have successfully applied 1,2,5-thiadiazoles as sources of nitrile sulfides recently, [9][10][11] thus 1,2,5-selenadiazoles have been selected for the present study as potential sources of nitrile selenides. It is important to note that PhCNSe was generated analogously from 3,4-diphenyl-1,2,5-selenadiazole and 3,5-diphenyl-1,2,4-selenadiazole earlier.…”

A theoretical study on the spectroscopy, structure, and stability of C2H3NS molecules

“…Calculations can be compared to limited experimental data as well. No IR spectra have been measured for the isomers 4-14, with the exception of the cryogenic argon matrix-isolated species 9 [64]. We limit our discussion here to 1, 2, and 3.…”

5th Heron Island Conference on Reactive Intermediates and Unusual Molecules

“…J. Chem. captures the flavour of the meeting by publishing 15 papers covering gold catalysis in organic synthesis, [2] corannulene-based curved p-radicals, [3] formation of 1,3-diradicals from bicyclic azo compunds, [4] electron spin resonance spectroscopy of a,n-didehydrotoluene diradicals, [5] allene-carbene conversion in the thioxanthene series, [6] nitrene and free radical intermediates from azidomethylacetophenones, [7] s-hole binding, [8] synthesis and reactions of cyclobutenimines, [9] development of methodology for natural product synthesis, [10] organic-inorganic composite nanoscale materials, [11] matrix isolation of nitrile sulfides, [12] unusual thioketenes and extended cumulenes, [13] mixed cyclophanes, [14] photoelectron spectroscopy of short-lived molecules containing Ge and As, [15] and the HERON reaction (Heteroatom rearrangements on nitrogen) of N-acyloxy-N-alkoxyamides. [16] We are pleased to acknowledge Dr Brett Schwartz for designing the cover art.…”

“…1), the Great Barrier Reef, Queensland, Australia, July [10][11][12][13][14][15][16]2010. [1] Heron Island is a small coral cay on the Tropic of Capricorn, 72 km north-east of Gladstone and 600 km north of Brisbane.…”