Ethenedithione Explained

Ethenedithione or ethylenedithone is an unstable chemical substance with formula S=C=C=S made from carbon and sulfur.

Ethenedithione can exist as a gas at low pressure and high temperature, but is unstable when condensed or under higher pressure.^[1]

It can be stabilized as a ligand binding two cobalt atoms.^[2]

Other occurrences as a ligand are in TpW(CO)₂(C₂S₂)^– and [TpW(CO)₂]₂Ni(C₂S₂)₂, where Tp is trispyrazolylborate.^[3]

Formation

Ethenedithione can be made by the flash vacuum pyrolysis of 2,5-Dithiacyclopentylideneketene.^[1]

Also it has been made by dissociative ionization of tetrathiapentalenedione, and then neutralisation of ions produced.^[4]

C₂S₂ is made along with carbon subsulfide and carbon monosulfide, in an electric discharge in carbon disulfide vapour.^[5]

Properties

In its ground state it is a triplet state (³Σ_g⁻).^[6] Ethenedithione can be trapped in a matrix of solid argon without decomposition.^[1]

The infrared spectrum contains a prominent line at 1179.3 cm⁻¹ due to asymmetric C=S stretch of the most common isotopes.^[1]

Over 60K, ethenedithione polymerises.^[7] Possible polymerisation products include polythiene.^[8]

Notes and References

1. Wentrup . Curt . Kambouris . Peter . Evans . Richard A. . Owen . David . Macfarlane . Graham . Chuche . Josselin . Pommelet . Jean Claude . Cheikh . Abdelhamid Ben . Plisnier . Michel . Flammang . Robert . 2,5-Dithiacyclopentylideneketene and ethenedithione, S:C:C:S, generated by flash vacuum pyrolysis . Journal of the American Chemical Society . April 1991 . 113 . 8 . 3130–3135 . 10.1021/ja00008a048.
2. Seidel . Wolfram W. . Meel . Matthias J. . Hughes . Stephen R. . Hupka . Florian . Villinger . Alexander . Ethenedithione (S=C=C=S): Trapping and Isomerization in a Cobalt Complex . Angewandte Chemie International Edition . 23 December 2011 . 50 . 52 . 12617–12620 . 10.1002/anie.201105055.
3. Zhang . Zhong . Pu . Liang . Li . Qian-shu . King . R. Bruce . The facile coupling of carbon monochalcogenides to ethenedichalcogenone ligands in binuclear iron carbonyl derivatives: a theoretical study . New J. Chem. . 2014 . 38 . 9 . 4282–4289 . 10.1039/C4NJ00740A.
4. Sülzle . Detlev . Schwarz . Helmut . Ethylenedithione(C2S2): Generation and Characterization by Neutralization-Reionization Mass Spectrometry . Angewandte Chemie International Edition in English . October 1988 . 27 . 10 . 1337–1339 . 10.1002/anie.198813371.
5. Bohn . Robert B. . Hannachi . Yacine . Andrews . Lester . Production and reactions of triplet CS: matrix infrared and ultraviolet spectra of C2S2 . Journal of the American Chemical Society . July 1992 . 114 . 16 . 6452–6459 . 10.1021/ja00042a024.
6. Ma . Ngai Ling . Wong . Ming Wah . 1998-12-31 . Ethenedithione (S=C=C=S): Does It Obey Hund's Rule? . Angewandte Chemie International Edition . en . 37 . 24 . 3402–3404 . 10.1002/(SICI)1521-3773(19981231)37:24<3402::AID-ANIE3402>3.0.CO;2-S . 1433-7851.
7. Yranzo . Gloria I. . Elguero . José . Flammang . Robert . Wentrup . Curt . Formation of Cumulenes, Triple-Bonded, and Related Compounds by Flash Vacuum Thermolysis of Five-Membered Heterocycles . European Journal of Organic Chemistry . June 2001 . 2001 . 12 . 2209–2220 . 10.1002/1099-0690(200106)2001:12<2209::AID-EJOC2209>3.0.CO;2-X.
8. Zmolek . Peter B. . Sohn . Honglae . Gantzel . Peter K. . Trogler . William C. . Photopolymerization of Liquid Carbon Disulfide Produces Nanoscale Polythiene Films . Journal of the American Chemical Society . 1 February 2001 . 123 . 6 . 1199–1207 . 10.1021/ja003200j.