Oxidations of sulfur rich heterocycles – new S-oxides of the parent 1,2,4-trithiolane and its tetramethyl derivative: synthesis and structural investigations

Petzold, Holm; Bräutigam, Silvio; Görls, Helmar; Weigand, Wolfgang; Uhlemann, Ute; Gessner, R.; Kiefer, W.; Majchrzak, Agnieszka; Mlostoń, Grzegorz

doi:10.1016/j.ica.2003.12.004

Cited by 13 publications

(21 citation statements)

References 21 publications

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“…The FeÀFe bond lengths found in 7a and 7c were 2.5075(5) and 2.5359(5) , respectively. The value for 7a was similar to that in the pdt (2.5103 (11) (18) ) was very similar to that calculated for the corresponding tetramethyl-1,2,4-trithiolane-4-oxide (1,48416 ) [8]. In complex 7c, the bond lengths Fe(1)ÀS (1) and Fe (2)ÀS (1), and the angle Fe(1)ÀS (1)ÀFe (2) could not be discussed due to the disorder mentioned above.…”

Section: ) [6f] [6i] [6l]supporting

confidence: 83%

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Oxidation of Diiron and Triiron Sulfurdithiolato Complexes: Mimics for the Active Site of [FeFe]‐Hydrogenase

Windhager

Seidel

Apfel

et al. 2008

Chemistry & Biodiversity

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The oxidation of the hexacarbonyl(1,3-dithiolato-S,S')diiron complexes 4a-4c with varying amounts of dimethyldioxirane (DMD) was systematically studied. The chemoselectivity of the oxidation products depended upon the substituent R (R=H, Me, 1/2 (CH2)(5)). For R=H, four oxidation products, 6a-6d, have been obtained. In the case of R=Me, three products, 7a-7c, were formed, and for R=1/2 (CH2)(5), only complex 8 was observed. These observations are due to steric and electronic effects caused by the substituent R. Additionally, oxidation of the triiron complex 5 with DMD was performed to yield the products 9a and 9b. X-Ray diffraction analyses were performed for 6a-6d, 7a, and 7c, as well as for 9a and 9b. The electronic properties were determined by density-functional theory (DFT) calculations.

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Section: ) [6f] [6i] [6l]supporting

confidence: 83%

“…This difference was caused by the radius contraction of S(1) in 6c, which was induced by the bonded O-atom O(1). The sulfenato S(1)ÀO (1) (18) ) lie in the expected range [8].…”

Section: ) [6f] [6i] [6l]mentioning

confidence: 91%

Oxidation of Diiron and Triiron Sulfurdithiolato Complexes: Mimics for the Active Site of [FeFe]‐Hydrogenase

Windhager

Seidel

Apfel

et al. 2008

Chemistry & Biodiversity

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“…15 In the case of 3,3,4,4-tetraphenylthietan-2-one (3a), the attempted oxidation with excess mCPBA in CH 2 Cl 2 at 50 °C over 18 h was reported to yield a mixture of products, but the expected S-oxide was not obtained. 16 In our experiments, 3a and 3e were treated with ca.…”

Section: Methodsmentioning

confidence: 99%

Thermal [2+2]-Cycloadditions of Diphenylketene with Aryl- and Hetaryl-Substituted Thioketones

Heimgartner¹,

Mlostoń²,

Urbaniak³

et al. 2015

HETEROCYCLES

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-The reaction of diphenylketene (1) with aryl-and hetaryl-substituted thioketones (2) gave the corresponding 3,3,4,4-tetraarylthietan-2-ones (3) in good yields. Remarkably, the reactions with bis-hetaryl-substituted thioketones occurred significantly faster compared with those involving the bis-aryl-substituted thioketones. The structure of compound 3c has been established by X-ray crystallography.

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“…Materials: 3,3,5,5‐Tetramethyl‐1,2,4‐trithiolane 1‐oxide ( 3b ) was prepared according to known protocols by oxidation of the corresponding 1,2,4‐trithiolane 1b using m ‐CPBA 5b. An analogous protocol was used for the preparation of 12 from commercially available di‐ tert ‐butyldisulfane 11…”

Section: Methodsmentioning

confidence: 99%

Thermolysis of 3,3,5,5‐Tetramethyl‐1,2,4‐trithiolane 1‐Oxide: First Matrix Isolation of the HOSS^· Radical

et al. 2012

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Flash vacuum pyrolysis of 3,3,5,5‐tetramethyl‐1,2,4‐trithiolane 1‐oxide performed at 700 °C yields the 1‐oxatrisulfan‐3‐yl radical (HOSS·) along with disulfur monoxide (S2O) and diisopropyl sulfide, which were isolated in argon matrices at 10 K. Upon irradiation with UV light, the 1‐oxatrisulfan‐3‐yl radical undergoes isomerization to the 1‐oxatrisulfan‐1‐yl radical (HSSO·). Both radicals were identified by comparison of their computed and experimental IR and UV/Vis spectra. In addition, density functional theory (DFT) computations offer a plausible explanation of the most likely reaction mechanism, suggesting that the initial step is a 1,3‐H shift with simultaneous ring opening. A 1‐oxatrisulfane derivative formed thereby undergoes fragmentations via a radical and a competitive concerted pathway leading to the observed final products. The same mechanism also governs the thermal fragmentation of di‐tert‐butyl disulfide S‐oxide. Its pyrolysis at 700 °C affords an analogous set of products, including the 1‐oxatrisulfan‐3‐yl radical (HOSS·) as the key intermediate.

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Oxidations of sulfur rich heterocycles – new S-oxides of the parent 1,2,4-trithiolane and its tetramethyl derivative: synthesis and structural investigations

Cited by 13 publications

References 21 publications

Oxidation of Diiron and Triiron Sulfurdithiolato Complexes: Mimics for the Active Site of [FeFe]‐Hydrogenase

Oxidation of Diiron and Triiron Sulfurdithiolato Complexes: Mimics for the Active Site of [FeFe]‐Hydrogenase

Thermal [2+2]-Cycloadditions of Diphenylketene with Aryl- and Hetaryl-Substituted Thioketones

Thermolysis of 3,3,5,5‐Tetramethyl‐1,2,4‐trithiolane 1‐Oxide: First Matrix Isolation of the HOSS^· Radical

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Oxidations of sulfur rich heterocycles – new S-oxides of the parent 1,2,4-trithiolane and its tetramethyl derivative: synthesis and structural investigations

Cited by 13 publications

References 21 publications

Oxidation of Diiron and Triiron Sulfurdithiolato Complexes: Mimics for the Active Site of [FeFe]‐Hydrogenase

Oxidation of Diiron and Triiron Sulfurdithiolato Complexes: Mimics for the Active Site of [FeFe]‐Hydrogenase

Thermal [2+2]-Cycloadditions of Diphenylketene with Aryl- and Hetaryl-Substituted Thioketones

Thermolysis of 3,3,5,5‐Tetramethyl‐1,2,4‐trithiolane 1‐Oxide: First Matrix Isolation of the HOSS· Radical

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Thermolysis of 3,3,5,5‐Tetramethyl‐1,2,4‐trithiolane 1‐Oxide: First Matrix Isolation of the HOSS^· Radical