Thioxoethenylidene Explained

Thioxoethenylidene, is a reactive heteroallene molecule with formula CCS.[1]

Occurrence

CCS is found in space in large quantities.[1] This includes the Taurus Molecular Cloud in TMC-1, TMC-1c and L1521B. These are likely in young starless molecular cloud cores.[2]

Production

By condensing propadienedithione SCCCS or thioxopropadienone OCCCS in solid argon and irradiating with ultraviolet radiation, CCS is formed.[1] Another way is via a glow discharge in a mixture of carbon disulfide and helium. Yet another way is through electron irradiation of sulfur containing heterocycles.[1]

CCS and the anion CCS can be formed in solid neon matrices also.[3]

Properties

CCS can be a ligand. It can form an asymmetrical bridge between two molybdenum atoms in Mo2(μ,σ(C):η2(C′S)-CCS)(CO)4(hydrotris(3,5-dimethylpyrazol-1-yl)borate)2 In this one carbon atom has a triple bond to a molybdenum and the other has a double bond to the other molybdenum atom, which also has a single bond to the sulfur atom.[4]

The ultraviolet spectrum shows absorption bands between 2800 and 3370 Å and also in the near infrared between 7500 and 10000 Å.[1] CCS can react with CCCS to form C5S.[1]

The infrared spectrum in solid argon shows a vibration band at 1666.6 cm−1 called v1 and another called v2 at 862.7 cm−1. The 2v1 overtone is at 3311.1  cm−1. A combination vibration and bending band is at 2763.4 cm−1[1]

The microwave spectrum has emission lines 43 − 32 at 45.4 GHz and 21 - 10 at 22.3 GHz, important for detection of molecules in molecular clouds.[2]

Theoretical predictions show that the C-C bond is 1.304 Å long and the C–S bond is 1.550 Å.[5]

Notes and References

  1. Maier. Günther. Reisenauer. Hans Peter. Ruppel. Raimund. Thioxoethenylidene C2S: A Matrix-Spectroscopic Study. European Journal of Organic Chemistry. October 2004. 2004. 20. 4197–4202. 10.1002/ejoc.200400252.
  2. Roy. Nirupam. Datta. Abhirup. Momjian. Emmanuel. Sarma. Anuj P.. Imaging of the CCS 22.3 GHz emission in the Taurus Molecular Cloud complex. 1106.4011. The Astrophysical Journal. 20 September 2011. 739. 1. L4. 10.1088/2041-8205/739/1/L4. 2011ApJ...739L...4R. 118857505.
  3. Riaplov. Evgueni. Wyss. Muriel. Maier. John P. Panten. Dietmar. Chambaud. Gilberte. Rosmus. Pavel. Fabian. Juergen. Electronic absorption spectra of CCS− and CCS in neon matrices. Journal of Molecular Spectroscopy. November 2003. 222. 1. 15–21. 10.1016/S0022-2852(02)00050-4. 2003JMoSp.222...15R.
  4. Caldwell. Lorraine M.. Hill. Anthony F.. Stranger. Robert. Terrett. Richard N. L.. von Nessi. Kassetra M.. Ward. Jas S.. Willis. Anthony C.. Thioxoethenylidene (CCS) as a Bridging Ligand. Organometallics. 12 January 2015. 34. 1. 328–334. 10.1021/om5011319. 1885/13701. free.
  5. Xie. Yaoming. Schaefer. Henry F.. Naked organosulfur clusters: The infrared spectrum of the C2S molecule. The Journal of Chemical Physics. March 1992. 96. 5. 3714–3717. 10.1063/1.461874. 1992JChPh..96.3714X.