Reactions of S atoms with dimethyl sulfide and thietane

Green, Martina; Lown, E. M.; Strausz, O. P.

doi:10.1021/ja00335a011

Cited by 22 publications

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“…The first step was the dimerization of phenylmethane thiol. This reaction has been reported by several previous studies, which indicated that the disulfide bond was formed by coupling two mercaptan groups. − Then, PhCH 2 S–SCH 2 Ph transformed into a (PhCH 2 ) 2 SS species by an intermolecular atomic rearrangement. This reaction mechanism has been observed by many previous experimental studies as well. ,− Lastly, the reaction of Au 15 (CH 3 ) 13 NC with the (PhCH 2 ) 2 SS species resulted in a Au 15 S(CH 3 ) 13 nanocluster …”

Section: Results and Discussionsupporting

confidence: 79%

“…This reaction has been reported by several previous studies, which indicated that the disulfide bond was formed by coupling two mercaptan groups. 78 − 83 Then, PhCH 2 S–SCH 2 Ph transformed into a (PhCH 2 ) 2 S=S species by an intermolecular atomic rearrangement. This reaction mechanism has been observed by many previous experimental studies as well.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Since the first reaction step has been confirmed by many experimental studies, 78 − 83 here we mainly focused on the second and the last reaction steps. As shown in Figure 4 a, isomerization of PhCH 2 S–SCH 2 Ph to (PhCH 2 ) 2 S=S proceeded via an intramolecular benzyl group migration by overcoming an energy barrier of 2.47 eV.…”

Section: Results and Discussionmentioning

confidence: 99%

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From Monolayer-Protected Gold Cluster to Monolayer-Protected Gold-Sulfide Cluster: Geometrical and Electronic Structure Evolutions of Au₆₀S_n(SR)₃₆ (n = 0–12)

Wang

Pei

2020

ACS Omega

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Thiolate-monolayer-protected gold clusters are usually formulated as Au N SR[Au(I)-SR] x , where Au N and SR[Au(I)-SR] x ( x = 0, 1, 2, ...) are the inner gold core and outer protection motifs, respectively. In this work, we theoretically envision a new family of S-atom-doped thiolate-monolayer-protected gold clusters, namely, Au 60 S n (SR) 36 ( n = 0–12). A distinct feature of Au 60 S n (SR) 36 nanoclusters (NCs) is that they show a gradual transition from the monolayer-protected metal NC to the SR[Au(I)-(SR)] x oligomer-protected gold-sulfide cluster with the increase of the number of doping S atoms. The possible formation mechanism of the S-atom-doped thiolate-protected gold cluster is investigated, and the size-dependent stability and electronic and optical absorption properties of Au 60 S n (SR) 36 are explored using density functional theory (DFT) calculations. It is found that doping of S atom significantly tails the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap and optical absorption properties of thiolate-protected gold cluster, representing a promising way to fabricate new monolayer-protected gold nanoparticles.

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Section: Results and Discussionsupporting

confidence: 79%

Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

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From Monolayer-Protected Gold Cluster to Monolayer-Protected Gold-Sulfide Cluster: Geometrical and Electronic Structure Evolutions of Au₆₀S_n(SR)₃₆ (n = 0–12)

Wang

Pei

2020

ACS Omega

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“…Figure 3A shows the spectrum of Au2(dppp)(pdt) before addition of Br2. After addition of one equivalent of Br2, the starting gold complex has disappeared and new peaks at 3.1 (triplet) and 2.25 (quintent) ppm due to 1,2-dithiolane 21 have appeared ( Figure 3B). The chemical shifts and appearance of the remaining peaks in Figure 3B are consistent with coordinated phosphine and are assigned as Au2(dppp)(Br)2 by comparison to an authentic sample of Au2(dppp)(CI)2 (see Figure 3C).…”

Section: Resultsmentioning

confidence: 99%

Redox Chemistry of Gold(I) Phosphine Thiolates: Sulfur‐BasedOxidation

et al. 1994

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The redox chemistry of mononuclear and dinuclear gold(I) phosphine arylthiolate complexes was recently investigated by using electrochemical, chemical, and photochemical techniques. We now report the redox chemistry of dinuclear gold(I) phosphine complexes containing aliphatic dithiolate ligands. These molecules differ from previously studied gold(I) phosphine thiolate complexes in that they are cyclic and contain aliphatic thiolates. Cyclic voltammetry experiments of Au2 (LL)(pdt) [pdt = propanedithiol; LL = 1,2-bis(diphenylphosphino)-ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), 1,5-bis(diphenylphosphino)pentane (dpppn)] in 0.1 M TBAH/CH3CN or CH2Cl2 solutions at 50 to 500 mV/sec using glassy carbon or platinum electrodes, show two irreversible anodic processes at ca. +0.6 and +1.1 V (vs. SCE). Bulk electrolyses at +0.9 V and +1.4 V result in n values of 0.95 and 3.7, respectively. Chemical oxidation of Au2(dppp)(pdt) using one equivalent of Br2 (2 oxidizing equivalents) yields 1,2-dithiolane and Au2(dppp)Br2. The reactivity seen upon mild oxidation ≤ +1.0 V is consistent with formal oxidation of a thiolate ligand, followed by a fast chemical reaction that results in cleavage of a second gold-sulfur bond. Oxidation at higher potentials (≥ +1.3 V) is consistent with oxidation of gold(I) to gold(III). Structural and electrochemical differences between gold(I) aromatic and aliphatic thiolate oxidation processes are discussed.

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“…Baechler et al reported the sulfuration of diallyl sulfide with S 8 in Me 2 SO-d 6 at 353-363 K. 19 Green et al also reported that S atoms reacted with CH 3 SCH 3 to generate elemental sulfur and CH 3 SSCH 3 as major primary products. 20 Under ultrasonic irradiation, S atoms may be released by the sonolysis of thioethers. 13,14 This result may be used to the ultrasonic desulfurization of sour crude oil.…”

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confidence: 99%

Ultrasonic Cleavage of Thioethers

Ondruschka

Stark

2005

J. Phys. Chem. A

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The rates of DPPH (diphenylpicrylhydrazyl) trapping and the sonolytical products obtained during the sonolysis of thioethers at normal and low temperature are reported. CS2, lower sulfides, thiophene, and sulfurized species are the common products during the ultrasonic irradiations. Hydrocarbons are also obtained during the sonolysis of diallyl sulfide, diethyl disulfide, and dipropyl disulfide. Furthermore, aldehydes are obtained as oxidized species; SO2 is found at 208 K. The principal sonochemical process appears to be the cleavage of C-S or S-S bond with secondary combinations and rearrangements. DPPH has been used to probe the sonolytical potential of thioethers. The results show a good correlation between the rates of DPPH trapping and the vapor pressures of thioethers. In conclusion, a lower vapor pressure results in a higher sonolytical rate. The sonochemical behaviors of thioethers have strong qualitative similarities to the pyrolysis.

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Reactions of S atoms with dimethyl sulfide and thietane

Cited by 22 publications

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From Monolayer-Protected Gold Cluster to Monolayer-Protected Gold-Sulfide Cluster: Geometrical and Electronic Structure Evolutions of Au₆₀S_n(SR)₃₆ (n = 0–12)

From Monolayer-Protected Gold Cluster to Monolayer-Protected Gold-Sulfide Cluster: Geometrical and Electronic Structure Evolutions of Au₆₀S_n(SR)₃₆ (n = 0–12)

Redox Chemistry of Gold(I) Phosphine Thiolates: Sulfur‐BasedOxidation

Ultrasonic Cleavage of Thioethers

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Reactions of S atoms with dimethyl sulfide and thietane

Cited by 22 publications

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From Monolayer-Protected Gold Cluster to Monolayer-Protected Gold-Sulfide Cluster: Geometrical and Electronic Structure Evolutions of Au60Sn(SR)36 (n = 0–12)

From Monolayer-Protected Gold Cluster to Monolayer-Protected Gold-Sulfide Cluster: Geometrical and Electronic Structure Evolutions of Au60Sn(SR)36 (n = 0–12)

Redox Chemistry of Gold(I) Phosphine Thiolates: Sulfur‐BasedOxidation

Ultrasonic Cleavage of Thioethers

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From Monolayer-Protected Gold Cluster to Monolayer-Protected Gold-Sulfide Cluster: Geometrical and Electronic Structure Evolutions of Au₆₀S_n(SR)₃₆ (n = 0–12)

From Monolayer-Protected Gold Cluster to Monolayer-Protected Gold-Sulfide Cluster: Geometrical and Electronic Structure Evolutions of Au₆₀S_n(SR)₃₆ (n = 0–12)