Cycloheptasulfur, S<sub>7</sub>, and Cyclodecasulfur, S<sub>10</sub> – Two New Sulfur Rings

Schmidt, Max; Block, B.; Block, Hans D.; Köpf, Hartmut; Wilhelm, Emmerich

doi:10.1002/anie.196806321

Cited by 70 publications

(16 citation statements)

References 8 publications

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“…A further progression to a selective synthesis of selenium rings at low temperature, used bis(cyclopentadienyl)titanium(IV) pentasulfide as reagent. It reacts with lower chlorosulfanes quantitatively under mild conditions as depicted in Equation . Changing S x Cl 2 in Equation to Se 2 Br 2 leads at 20 °C to SeS 5 which partly dimerizes to 1,2‐Se 2 S 10 and 1,7‐Se 2 S 10 .…”

Section: Resultsmentioning

confidence: 99%

A New Look on Larger Sulfur and Selenium Rings – Dispersion Forces and Shapes of Larger Cycles

2019

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In this paper we discuss the shape of sulfur and selenium rings S6 to S20 and Se6 to Se20. The sizes and conformations of the sulfur rings are known by X‐ray data. A comparison between the results of B3LYP/cc‐pVTZ, B3LYP‐D3/cc‐pVTZ, and B3LYP‐D3BJ/cc‐pVTZ calculations reveals structural relaxation dispersion energy values of 3.0 kJ/mol (S10) and 19.4 kJ/mol (S18) for the sulfur allotropes. In the case of selenium rings, we investigated rings with the same size. We found that at low temperatures the selenium rings Se13, Se14, Se18 and Se20 should be more stable than Se8 if the empirical dispersion corrections D3 and D3BJ are taken into account. All larger rings reveal structural relaxation dispersion between 6.0 kJ/mol (Se10) and 34.7 kJ/mol (Se18). Furthermore, the calculations reveal that the consideration of the dispersion energy using the correction terms D3 and D3BJ leads in some cases to a distortion of the molecular structure accompanied by a degradation of the molecular symmetry. In these cases, the transannular distances strongly depend on the method used and the difference sometimes amounts to more than 1 Å. For the structural relaxation dispersion energy, the following applies: A few short noncovalent bonds are better than many medium‐sized ones. The structural distortion is also found in the X‐ray data which stresses the importance of the usage of the dispersion correction terms for the structural investigation of these cycles.

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Section: Resultsmentioning

confidence: 99%

A New Look on Larger Sulfur and Selenium Rings – Dispersion Forces and Shapes of Larger Cycles

2019

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“…The sulfur homocycles were detected by a UV detector (JASCO UVDEC 100-VI) at 265 nm at a flow rate (1 ml/min) of the mobile phase (20% cyclohexane-methanol so lution). The working curve for S7 was con structed using a pure S7 fraction separated chro matographically from a synthesized mixture of S7 and a few % S8 (Schmidt et al, 1968). This pro cedure was conducted as follows: molten sulfur at 200°C was gradually cooled down to 159°C, then quenched rapidly by pouring the melt into liquid nitrogen.…”

Section: Chemical Analysismentioning

confidence: 99%

Geochemical implications of subaqueous molten sulfur at Yugama crater lake, Kusatsu-Shirane volcano, Japan.

1994

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Crater lakes with active subaqueous fumaroles often contain molten sulfur pools on the lake floor. Volcanic gases passing through the sulfur pools carry hollow spherules of solidified molten sulfur to the surface of crater lakes. This sulfur dissolves SO2 and H2S gases and releases these gases into the water. The sulfur also contains homocyclic sulfur (cycl. S, x = 6-16) and probably sulfane monosulfonates. The concentration of cyclic S7 increases with increasing temperature between 120 and 175°C, which is useful to estimate the temperatures of subaqueous molten sulfur pools. The gases drastically lower viscosity of the molten sulfur. This may be due to blockage of growing long-chain sulfur molecules by the dissolved gases. Thus a jump in viscosity at 159°C observed for pure sulfur is not likely to be present in subaqueous molten sulfur at crater lakes. Based on the chemistry and morphology of sulfur slicks, activity of subaqueous fumaroles can be divided into four stages (I-IV), each of which may serve for qualitative in situ monitoring of crater lakes. At Stage I, no molten sulfur pools exist on the lake floor and fumaroles discharge low temperature gases (<119°C) containing only traces of SO2; at Stage II, subaqueous molten sulfur pools (119°C < T < 150°C) are formed, releasing yellow hollow spherules of sulfur with no tails; at Stage III, the fumarolic temperature increases to >150°C, resulting in an increase in molten sulfur viscosity; and at Stage IV, frequent phreatic or geyser-like eruptions are observed. The molten sulfur pools are dispersed into pieces on the lake floor at this stage.

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“…Titanocenium polysulfido complexes convert with S x Cl 2 ( x =1–2) to give cyclic polysulfanes as well as titanium dichlorido complexes (Scheme ) . For example, a reaction of [Cp 2 Ti(S 5 )] ( 22 ) with SCl 2 yields S 6 and S 12 , whereas with S 2 Cl 2 S 7 is formed . Mechanistically, Steudel and co‐workers proposed the initial generation of intermediates like [Cp 2 TiCl(S 5+ x Cl)] ( 24 ), which either eliminate the cyclic sulfur molecules S 6 ( x =1) and S 7 ( x =2) or react for x =1 with another equivalent of [Cp 2 Ti(S 5 )] ( 22 ) and subsequently SCl 2 generating S 12 (Scheme ) .…”

Section: Sulfur(i)/(ii) Compoundsmentioning

confidence: 99%

Reactivity of Binary and Ternary Sulfur Halides towards Transition‐Metal Compounds

Dirican

Pfister

Wozniak

et al. 2020

Chemistry A European J

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Binary sulfur fluorides exhibit an interesting reactivity towards transition metal complexes. They open up routes for the generation of sulfur‐containing building blocks. Often ligands with particular properties can be constructed. This includes their ability to transfer sulfur atoms or polysulfide units as well as fluorination reactions. This Minireview provides an insight into the reactivity of the binary and ternary sulfur halides S2Cl2, SCl2, SF4, SF6 and SF5Cl towards transition‐metal compounds.

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Cycloheptasulfur, S₇, and Cyclodecasulfur, S₁₀ – Two New Sulfur Rings

Cited by 70 publications

References 8 publications

A New Look on Larger Sulfur and Selenium Rings – Dispersion Forces and Shapes of Larger Cycles

A New Look on Larger Sulfur and Selenium Rings – Dispersion Forces and Shapes of Larger Cycles

Geochemical implications of subaqueous molten sulfur at Yugama crater lake, Kusatsu-Shirane volcano, Japan.

Reactivity of Binary and Ternary Sulfur Halides towards Transition‐Metal Compounds

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Cycloheptasulfur, S7, and Cyclodecasulfur, S10 – Two New Sulfur Rings

Cited by 70 publications

References 8 publications

A New Look on Larger Sulfur and Selenium Rings – Dispersion Forces and Shapes of Larger Cycles

A New Look on Larger Sulfur and Selenium Rings – Dispersion Forces and Shapes of Larger Cycles

Geochemical implications of subaqueous molten sulfur at Yugama crater lake, Kusatsu-Shirane volcano, Japan.

Reactivity of Binary and Ternary Sulfur Halides towards Transition‐Metal Compounds

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Cycloheptasulfur, S₇, and Cyclodecasulfur, S₁₀ – Two New Sulfur Rings