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Sodium 1,3-dithiole-2-thione-4,5-dithiolate

Sodium 1,3-dithiole-2-thione-4,5-dithiolate is the organosulfur compound with the formula Na<sub>2</sub>C<sub>3</sub>S<sub>5</sub>, abbreviated Na<sub>2</sub>dmit. It is the sodium salt of the conjugate base of the 4,5-bis(sulfanyl)-1,3-dithiole-2-thione. The salt is a precursor to dithiolene complexes and tetrathiafulvalenes.

Reduction of carbon disulfide with sodium affords sodium 1,3-dithiole-2-thione-4,5-dithiolate together with sodium trithiocarbonate:

4 Na + 4 CS<sub>2</sub> → Na<sub>2</sub>C<sub>3</sub>S<sub>5</sub> + Na<sub>2</sub>CS<sub>3</sub>

Before the characterization of dmit<sup>2-</sup>, reduction of CS<sub>2</sub> was thought to give tetrathiooxalate (Na<sub>2</sub>C<sub>2</sub>S<sub>4</sub>).

The dianion C<sub>3</sub>S<sub>5</sub><sup>2-</sup> is purified as the tetraethylammonium salt of the zincate complex [Zn(C<sub>3</sub>S<sub>5</sub>)<sub>2</sub>]<sup>2-</sup>. This salt converts to the bis(thioester) upon treatment with benzoyl chloride:

[N(C<sub>2</sub>H<sub>5</sub>)<sub>4</sub>]<sub>2</sub>[Zn(C<sub>3</sub>S<sub>5</sub>)<sub>2</sub>] + 4 C<sub>6</sub>H<sub>5</sub>COCl → 2 C<sub>3</sub>S<sub>3</sub>(SC(O)C<sub>6</sub>H<sub>5</sub>)<sub>2</sub> + [N(C<sub>2</sub>H<sub>5</sub>)<sub>4</sub>]<sub>2</sub>[ZnCl<sub>4</sub>]

Cleavage of the thioester with sodium methoxide gives sodium 1,3-dithiole-2-thione-4,5-dithiolate:

C<sub>3</sub>S<sub>3</sub>(SC(O)C<sub>6</sub>H<sub>5</sub>)<sub>2</sub> + 2 NaOCH<sub>3</sub> → Na<sub>2</sub>C<sub>3</sub>S<sub>5</sub> + 2 C<sub>6</sub>H<sub>5</sub>CO<sub>2</sub>Me

Na<sub>2</sub>dmit undergoes S-alkylation. Heating solutions of Na<sub>2</sub>dmit gives the isomeric 1,2-dithioledithiolate.

References