The chemistry of dithietes, 1,2,5,6-tetrathiocins and higher oligomers

Abstract

The synthesis and reactivity patterns of the strained dithiete ring are compared with their dimeric tetrathiocin counterparts and higher oligomers, highlighting: (i) their cycloaddition chemistry with organic dienophiles as a...

Synthesis, Structure and Reactivity of Organoindium 1,2‐Benzenedithiolates and 2‐Amidobenzenethiolates

“…[39] It has been previously reported that 1,2-benzenedithiol is slowly oxidized by I 2 to yield 1,2,5,6-tetrathiocin and a variety of other poorly soluble oligomers. [40][41][42] Our reaction of H 2 tdt with 0.5 equivalents of I 2 for 19 h in thf-d 8 resulted in the formation of peaks 2.20, 6.98 and 7.43 ppm in the 1 H NMR spectrum, which is similar to those observed in the reaction of 1 with I 2 . The formation of oligomeric [tdt] n is further suggested by the poor solubility of the product in organic solvents other than thf and the reported solubility and recrystallization of [tdt] 2 in benzene.…”

“…The presence of small peaks at 2.30 and 2.35 ppm in the 1 H NMR spectra suggests the formation of a small amount of the two isomers of 1,2,5,6‐tetrathiocin [tdt] 2 [39] . It has been previously reported that 1,2‐benzenedithiol is slowly oxidized by I 2 to yield 1,2,5,6‐tetrathiocin and a variety of other poorly soluble oligomers [40–42] . Our reaction of H 2 tdt with 0.5 equivalents of I 2 for 19 h in thf‐ d 8 resulted in the formation of peaks 2.20, 6.98 and 7.43 ppm in the 1 H NMR spectrum, which is similar to those observed in the reaction of 1 with I 2 .…”

“…The oxidation of the tdt ligand in 1 and 2 to yield 1,2,5,6‐tetrathiocin [tdt] 2 and oligomeric [tdt] n and the formation of indium iodide species rather than the oxidized species 1 ⋅ + − 4 ⋅ + was unexpected. It has been shown that 1,2‐benzenedithiols are oxidized by I 2, SOCl 2 or the superoxide ion to yield 1,2,5,6‐tetrathiocins, [39–42] Further, oxidative coupling of 1,2‐dithiolate ligands of metal complexes to afford novel 1,2,5,6‐tetrathiocins has also been reported. For example, Na 2 (C 2 S 5 ) may be oxidized with Me 2 TeCl 2 or [Et 4 N] 2 [Zn(C 3 S 5 ) 2 ] with SO 2 Cl 2 to afford C 6 S 10 in moderate yields [46,47] .…”

Synthesis, structural peculiarities, and photosensitivity of fluorinated dibenzo-1,2,5,6-tetrathiocines

“…1,2,5,6-Tetrathiocines, [1][2][3][4][5][6][7][8] their Se analogues, [2][3][4][5][8][9][10][11][12] and S/Se hybrids 4,5,7 are structurally-flexible eight-membered heterocycles most known with fused (benzo, pyrrolo, thiopheno) derivatives; any Te congeners are not reported. The compounds are relatively less-studied, meanwhile they are of current interest due to chemical reactivity embracing synthesis of new materials; and S incarnations, also due to bioactivity.…”

Oxidative addition of 1,2,5,6-Tetrathiocins to Co(I): A Re-Examination of Crown Ether Functionalized Benzene Dithiolate Cobalt(III) Complexes

“…Their synthetic method is lengthy, and several intermediates were incompletely characterized and/or yields not reported. , An alternative synthetic strategy to access dithiolate complexes is the oxidative addition of dithietes to low-valent metals . This methodology has recently been exploited by Fekl and Kuropatov who examined oxidative addition of dithietes to Pd(0). , In this context, we have explored the related benzo-fused1,2,5,6-tetrathiocins which can be considered as dimers of the dithiete moiety and exhibit similar reactivity to zero-valent group 10 metal complexes. − …”