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

Watanabe, Lara K.; Wrixon, Justin D.; Rawson, Jeremy M.

doi:10.1039/d1dt02760c

Cited by 3 publications

(4 citation statements)

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“…[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.…”

Section: Reactivity With Oxidantssupporting

confidence: 71%

“…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 .…”

Section: Resultsmentioning

confidence: 86%

“…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] .…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2022

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Organoindium compounds of redox active 1,2-benzenedithiolate and 2-amidobenzenethiolate ligands were synthesized and tested for reactivity against mild oxidants. The reaction of Me 3 In and (NCN)InMe 2 [NCN = 2,6-bis(dimethylaminomethy)phenyl] with 3,4-toluenedithiol (H 2 tdt) at room temperature afforded [MeIn(tdt)(py)] 2 (1) and (NCN)In(tdt) (2), respectively. A similar reaction of Me 3 In with 2-aminobenzenethiol (H 2 abt) in toluene under reflux afforded [MeIn(abt)(py)] 2 (3). The reaction of (NCN)InCl 2 with one equivalent of Li 2 (abt) or two equivalents of Li(Habt) afforded the compounds [(NCN)In(abt)]•LiCl(thf) 2 (4•LiCl(thf) 2 ) and (NCN)In(Habt) 2 (5), respectively. The X-ray crystal structures of 1 and 3 are similar and show dimeric structures via μ-S-(tdt) and μ-N-(abt) ligands, respectively. Compounds 2 and 4 possess similar monomeric structures and tridentate NCN pincer ligands. DFT computational studies have been used to rationalize the observed solid-state structures and discern the potential reactivity of compounds 1-4 against oxidants. The reaction of 1 and 2 with excess iodine resulted in loss of the 3,4-toluenedithiolate ligand and the formation of the oligomeric disulfide [tdt] n , while 3 and 4 showed no reactivity under similar conditions. This contrasts the reactivity of previously reported organoindium o-amidophenolate complexes which undergo oxidative addition of iodine to afford ligand-centered radical species.

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Section: Reactivity With Oxidantssupporting

confidence: 71%

Section: Resultsmentioning

confidence: 86%

Section: Resultsmentioning

confidence: 99%

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

et al. 2022

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“…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. − …”

Section: Introductionmentioning

confidence: 99%

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

et al. 2022

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Oxidative addition of the 4′,4″,5′,5″-crown-functionalized dibenzo-1,2,5,6-tetrathiocins, [(OCH 2 CH 2 ) n OC 6 H 2 S 2 ] 2 (1, n = 4; 2, n = 5), to the Co(I) complex CpCo(CO) 2 under microwave irradiation in toluene affords 16e − Co(III) dithiolate complexes CpCo{S 2 C 6 H 2 O(CH 2 CH 2 O) n } 3 (n = 4) and 4 (n = 5) in 71−75% recovered yield. Complexes 3 and 4 were characterized by X-ray diffraction. Compound 3 was found to be polymorphic, crystallizing as the 16e − monomer, 3, or the 18e − dimer, (3) 2 , depending upon reaction conditions. In contrast to previous literature which suggested formation of 1:1 complexes between 3 and s-block cations, reaction of 3 with the s-block metal salts M[BPh 4 ] (M = Na, K, Rb, and Cs) formed the 2:1 complexes [{CpCo(S 2 C 6 H 2 O-(CH 2 CH 2 O) 4 )} 2 M][BPh 4 ] (5a−5d, respectively) whose structures were determined by X-ray diffraction and revealed that the alkali metal ion is sandwiched by two crown ether substituents in all cases. UV/vis titration studies of complex 3 with NaBPh 4 were consistent with formation of the 2:1 complex as the dominant species in solution. Mass spectrometry studies on 5a−5d revealed the presence of both [(3) 2 M] + and [(3)M] + ions (M = Na, K, Rb, and Cs). Electrochemical studies on 3 revealed an irreversible 1e − oxidation attributed to a ligand-based process based on DFT calculations. Chemical oxidation of 3 afforded two dimeric structures [{CpCo(S 2 C 6 H 2 O(CH 2 CH 2 O) 4 )} 2 ][X] 2 (6a, X = OTf; 6b, X = BF 4 ) in which dithiolate ligand oxidation leads to complexes containing a disulfide bond, consistent with electrochemical and computational studies.

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The literature of heterocyclic chemistry, Part XXI, 2021

Belen’kii,

Gazieva,

Evdokimenkova

et al. 2024

Advances in Heterocyclic Chemistry

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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...

Cited by 3 publications

References 105 publications

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

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

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

The literature of heterocyclic chemistry, Part XXI, 2021

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