New carbon sulfides based on 4,5-dimercapto-1,2-dithiole-3-thione (.beta.-C3S52-): [C3S5]n, C6S8, and C5S7

Abstract

This investigation centers on the preparation of new binary carbon sulfides based on the 1,2-dithiole-3-thione subunit as found in the precursor dithiolate C3S5* 12'. Tricyclic CeSg, 1, was obtained in high yield by thermal elimination of H2S from the dimercaptan J8-C3S5H2. A crystallographic study confirmed a tricyclic structure of idealized D2a symmetry containing an unusual planar 1,4-dithiin unit. The crystals of 1 are monoclinic, space group P2\/c, with a = 8. 046(2), b = 9.797(3), c = 13.818(4) Á, V-1048.3(9) Á3 4, andZ = 4. The final R and Rw values were 0.036 and 0.042, respectively. The bicyclic carbon sulfide C5S7,3, was prepared from reduction of C4S6,2, with LiBEtsH, followed by addition of thiophosgene. Oxidation of CP2TÍOS-C3S5) or Zn(/3-C3S¡)22~w ith SO2CI2 afforded [¿J-C3S5],,, 4, an orange insoluble solid. Degradation of [y-CsSs], with dimethyl acetylenedicarboxylate (DMAD) afforded C3S5-2DMAD, 5, together with small amounts of C3S5 3DMAD, 6. The single-crystal X-ray structure of C3S5 -2DMAD revealed a folded 1,4-dithiin linked to a planar 1,3-dithiole. Crystals of 5 are monoclinic, space group Cc, with a = 18.760(4), b = 13.664(3), c = 7.880(2) k,V = 1957(2) Á3, and Z = 4. The least-squares refinement with anisotropic thermal parameters for all non-hydrogen atoms converged at R -0.036 and i?w = 0.047. The DMAD treatment proceeds in a similar manner with [M(/3-C3Ss)2]2~(M = Zn, Ni) to yield [M^Ss'DMADh]2-.The C3S5 DMAD ligand can subsequently be removed from the zinc complex by reaction with thiophosgene giving bicyclic C4S6 DMAD, which can also be obtained via Cp2Ti(C3Ss-DMAD).

Three polymorphs of bis(5‐methylthio‐1,2‐dithiole‐3‐thione)‐disulfide

“…Selected torsion angles (°): C2-S4-S14-C12 97.8(2), C3-C2-S4-S14 -101.6(4), C13-C12-S14-S4 -97.4(4). C2-S4-S14-C12 -72.52 (14), C3-C2-S4-S14 -79.1(2), C13-C12-S14-S4 -80.4 (2).…”

“…1,2-Dithiole-3-thione-4,5-dithiole [1] is a well-known ligand in the coordination chemistry. Additionally, the 1,2-dithiole-4-thione subunit is an interesting precursor to yield binary carbon sulfides as C 5 S 7 or C 6 S 8 [2]. Disulfurization of the bis-methylsubstituted compound furnished a thiodesaurine [3].…”

Diverse reactivities of aromaticity–unsaturation coexisted metalladithiolene rings

“…A possible intermediate, intraligand S,S 0 -cycloadduct, was not isolated. Rauchfuss et al reported that the reaction of DMAD with the dianionic [M(dmt) 2 ] 2À (M ¼ Zn, Ni (9); dmt ¼ 1,2-dithiol-3-thione-4,5-dithiolate) or with [Cp 2 Ti(dmt)] 0 underwent the cycloaddition at the trithiocarbonate moiety to form the ligand centered cycloadduct (10) [39] (Chart 8 (b)). This reaction is also typical for an organic trithiocarbonate compound with acetylene.…”

“…In addition, electrophilic acetylene compounds ReC^CeR, where R ¼ CO 2 Me or CO 2 Et, react with 27 [80], 29 [81], 30 [43] or 32 [82] to form the corresponding alkene-bridged adducts (41, 43e45, Scheme 3 (b,c)). In addition, [Cp*Co(dcmedt)] (39), which should be more electron-rich than the Cp complex, reacts with ReC^CeR giving the alkene adduct (42), although the CpCo analog 26 does not produce it well. Diphenylacetylene (PheC^CePh) does not react with those dithiolene complexes.…”

Synthesis, characterization and crystal structure of dicesium bis(1,2-dithiole-3,5-dithiolato-4-yl)disulfide

“…However 6 is a 5,5-disulfide rather than the 4,4-disulfide type, 3, we have obtained. Further reported oxidized [dmt] derivatives are a polymeric species [dmt] n , via oxidation of metal salts of [dmt] 2À with SO 2 Cl 2 [11] and a monomeric bis-disulfide, 7, via oxidation with I 2 or TCNQ [12]. No confirmation of the aggregation state of either [dmt] n or 7 however have been given.…”