Synthesis and Structure of the Sulfur-Rich Macrocycle (1,2-C6H4S8)2

Abstract

Benzenebis(sulfenyl chloride) and the zinc complex (TMEDA)ZnS6 react at 25 °C to give the 20‐membered heterocycle (C6H4S8)2 in addition to the monomer 1,2‐C6H4S8.

The Chemistry of Organic Polysulfanes R−Sn−R (n > 2)

“…For example, 1,2-benzene-bis(sulfenyl chloride) on treatment with 16 yields the ten-membered bicycle 1,2,3,4,5,6,7,8-benzooctathiecin 17 (60% yield) 49 and, under slightly different conditions, the macrocycle (1,2-C 6 H 4 S 8 ) 2 , which is formally the dimer of 17 (Scheme 2). 167 Since similar zinc complexes with differing number of sulfur atoms in the metallacycle are known (depending on the amine used), 168 their reactions with sulfenyl chlorides will probably provide access to more sulfur-rich heterocycles in the future.…”

“…This enumeration includes also systems with two independent S n units (n ) 2-8) in one ring, bridged by carbon atoms. The following are leading references: trisulfanes; 125,130,162,171,[222][223][224] bis-trisulfane; 225 tetrasulfanes; [226][227][228] bis-tetrasulfane; 229 pentasulfanes; 122,130,142,148,171,[230][231][232][233] bis-pentasulfane; 163 hexasulfanes; 148,233 heptasulfane; 47 octasulfanes; 167,175 nonasulfane; 174 undecasulfane. 157 The geometrical parameters of the S n units in cyclic organic polysulfanes may be quite different from those in chain-like compounds since the ring closure may enforce unusual valence and torsional angles and, as a consequence, the bond distances will be affected.…”

“…177 (d) Larger rings either adopt the same conformation as the corresponding sulfur homocycles S 8 (D 4d ), 240 S 9 (C 1 ) , 105 S 10 (D 2 ), 241 S 11 (C 1 ), 242 and S 12 (D 3d ) 243 or are of lower symmetry. In the following, only the ring size and ring composition are given: 8: C 4 S 4 , 162 C 2 S 6 , 244 CS 7 186,245 9: CS 8 , 175 C 4 S 5 148 10: C 4 S 6 162,225 11: C 2 S 9 174 12: CS 11 157 >12: 167,229 For structures of bicyclic tetrasulfanes, see ref 227. The structures of some carbon polysulfide anions (e.g., C 4 S 8 2-, C 16 S 18 4-) have also been investigated crystallographically.…”

“…The zinc complex (TMEDA)ZnS 6 16 has also been used successfully in the preparation of sulfur-rich organic polysulfanes (TMEDA = tetramethylethenediamine). For example, 1,2-benzene-bis(sulfenyl chloride) on treatment with 16 yields the ten-membered bicycle 1,2,3,4,5,6,7,8-benzooctathiecin 17 (60% yield) 49 and, under slightly different conditions, the macrocycle (1,2-C 6 H 4 S 8 ) 2 , which is formally the dimer of 17 (Scheme ) 2 …”

“…This enumeration includes also systems with two independent S n units ( n = 2−8) in one ring, bridged by carbon atoms. The following are leading references: trisulfanes; ,,,,− bis-trisulfane; tetrasulfanes; − bis-tetrasulfane; pentasulfanes; ,,,,,− bis-pentasulfane; hexasulfanes; , heptasulfane; octasulfanes; , nonasulfane; undecasulfane …”