Bis(trimethylsilyl)sulfide explained
Bis(trimethylsilyl) sulfide is the chemical compound with the formula ((CH3)3Si)2S. Often abbreviated (tms)2S, this colourless, vile-smelling liquid is a useful aprotic source of "S2−" in chemical synthesis.[1]
Synthesis
The reagent is prepared by treating trimethylsilyl chloride with anhydrous sodium sulfide:[2]
2 (CH3)3SiCl + Na2S → ((CH3)3Si)2S + 2 NaCl
((CH3)3Si)2S must be protected from air because it hydrolyzes readily:
((CH3)3Si)2S + H2O → ((CH3)3Si)2O + H2S
Use in synthesis
Bis(trimethylsilyl)sulfide is a reagent for the conversion of metal oxides and chlorides into the corresponding sulfides.[3] This transformation exploits the affinity of silicon(IV) for oxygen and halides. An idealized reaction is:
((CH3)3Si)2S + MO → ((CH3)3Si)2O + MSIn a similar way, it has been used in the conversion of aldehydes and ketones to the corresponding thiones.[4] [5]
Safety
((CH3)3Si)2S reacts exothermically with water, releasing toxic H2S.
Notes and References
- Matulenko, M. A. . Bis(trimethylsilyl) Sulfide. Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette), J. Wiley & Sons, New York . 2004 . 10.1002/047084289X . 1 . 5. 10261/236866 . 9780471936237. free .
- Book: So, J.-H. . Boudjouk, P. . Hexamethyldisilathiane . Inorganic Syntheses . Russell, N. G. . 1992 . 29 . 0-471-54470-1 . 10.1002/9780470132609.ch11 . 30 . Wiley . New York.
- Lee, S. C.; Holm, R. H., "Nonmolecular Metal Chalcogenide/Halide Solids and Their Molecular Cluster Analogues", Angewandte Chemie International Edition in English, 1990, volume 29, pages 840-856.
- Synthetic Applications of Bis(trimethylsilyl)sulfide: Part II. Synthesis of Aromatic and Heteroaromatic o-Azido-Thioaldehydes. A. Capperucci . A. Degl'Innocenti . P. Scafato . P. Spagnolo . Chemistry Letters. 24. 147. 1995. 10.1246/cl.1995.147. 2.
- Some Recent Synthetic Routes to Thioketones and Thioaldehydes. W. M. McGregor . D. C. Sherrington . Chemical Society Reviews. 22. 199–204. 1993. 10.1039/CS9932200199. 3.
