Further evidence for existence of the Mills‐Nixon Effect ‐ <i>ab initio</i> study of the electrophilic reactivity in heteroanalogs of benzocyclopropene

Maksić, Zvonimir B.; Kovaček, Damir; Kovačević, Borislav

doi:10.1002/ejtc.11

Cited by 2 publications

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References 23 publications

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“…Trisulfides can also result from the insertion of S 2 into a disulfide, followed by the extrusion of atomic sulfur. 78 It has been observed that benzyne, generated by thermolysis of diphenyliodonium-2-carboxylate, reacted with sulfur to give benzopentathiepin and thianthrene, suggesting an initial formation of benzothiirene (o-C 6 H 4 S) (Figure 6), 79,80 that exhibits enhanced selectivity in electrophilic substitution reactions, 81 and has also been postulated as intermediate in the thermolysis of sodium o-bromobenzenethiolates. The mechanism involving consecutive reactions from the primordial extrusion of monatomic sulfur of the episulfide, considers reactions between reactive sites.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…It has been observed that benzyne, generated by thermolysis of diphenyliodonium-2-carboxylate, reacted with sulfur to give benzopentathiepin and thianthrene, suggesting an initial formation of benzothiirene ( o -C 6 H 4 S) (Figure ), , that exhibits enhanced selectivity in electrophilic substitution reactions, and has also been postulated as intermediate in the thermolysis of sodium o -bromobenzenethiolates …”

Section: Resultsmentioning

confidence: 99%

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Reactive Site Model of the Reduction of SO₂ on Graphite

Humeres¹,

Debacher²,

Moreira³

et al. 2017

J. Phys. Chem. C

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Computational quantum chemistry calculations were carried out for the reduction of SO2 on graphite to produce elemental sulfur and CO2. Two models of the reactive site of graphite were used and a viable mechanism was proposed for the reaction pathways based on experimental results and known reactions. The SO2 OO approach to the zigzag edge of the model cluster yielded a sulfur-oxidized intermediate 1,3,2-dioxathiolane (1). Sulfur transfer step takes place from 1 to a neighbor benzyne site forming a reduced sulfur intermediate thiirene (2) along with a 1,3-dicarbonyl in equilibrium with the peroxide valence tautomer. The calculated barrier from 1 to thiirene 2 at 900 °C was 39.4, kcal mol–1. The peroxide tautomer isomerizes to a dioxirane intermediate that is eliminated as dioxicarbene to produce CO2. The total free energy of activation for the decarboxylation reaction at 900 °C was in the range 110.8–122.7 kcal mol–1 depending on the model (ΔG ‡ experimental, 114.3 kcal mol–1). The reduced intermediate thiirene 2 decomposes through a transport mechanism where polysulfane species with increasing number of sulfur atoms eleminate elemental S x .

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