On the sulfur-nitrogen bonding character of N-arylsulfilimines

Tsuchiya, Soji; Mitomo, Shun-ichi; Senō, Manabu; Miyamae, Hiroshi

doi:10.1021/jo00193a020

Cited by 17 publications

(5 citation statements)

References 2 publications

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“…Comparable experimental data are not available for sulfilimines (nitrogen ylides) or S , C -sulfonium ylides (carbon ylides), although discussion of the type of bonding in sufilimines, parallel to the descriptions of sulfoxides, has appeared. ,, An older study estimated the BDE of the S−CH 2 bond in H 2 SCH 2 to be 27.5 kcal/mol with use of MP3/6-31G(d,p), but a more recent G2 calculation for dimethylsulfonium methylide put the BDE at 51 kcal/mol for dissociation to singlet methylene, which is about 9 kcal/mol above the triplet methylene ground state. To the best of our knowledge, there are no reports on the BDEs of sulfilimines or selenoxides.…”

Section: Introductionmentioning

confidence: 99%

Sulfur and Selenium Ylide Bond Enthalpies

et al. 2007

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The bond dissociation enthalpies (BDEs) of sulfur and selenium ylides have been estimated by applying MP2/6-311++G(3df,2p)//MP2/6-31G(d,p), G3, and other computational methods. Computed sulfoxide bond enthalpies were compared to experimental results to ensure the reliability of the computational methods before extending to related compounds. The examined ylides include the following: sulfoxides, sulfilimines, S,C-sulfonium ylides, and selenoxides. Selenoxides have BDEs about 10 kcal/mol smaller than the corresponding sulfoxides. N-H sulfilimines and CH2-S,C-sulfonium ylides have low BDEs, unless the sulfilimine or S,C-sulfonium ylide is stabilized by an electronegative substituent on N or C, respectively. Incorporation of the S or Se into a thiophene or selenophene-type ring lowers the BDE for the ylide. DisciplinesChemistry | Organic Chemistry | Other Chemistry | Polymer Chemistry CommentsReprinted (adapted) The bond dissociation enthalpies (BDEs) of sulfur and selenium ylides have been estimated by applying MP2/6-311++G(3df,2p)//MP2/6-31G(d,p), G3, and other computational methods. Computed sulfoxide bond enthalpies were compared to experimental results to ensure the reliability of the computational methods before extending to related compounds. The examined ylides include the following: sulfoxides, sulfilimines, S,C-sulfonium ylides, and selenoxides. Selenoxides have BDEs about 10 kcal/mol smaller than the corresponding sulfoxides. N-H sulfilimines and CH 2 -S,C-sulfonium ylides have low BDEs, unless the sulfilimine or S,C-sulfonium ylide is stabilized by an electronegative substituent on N or C, respectively. Incorporation of the S or Se into a thiophene or selenophene-type ring lowers the BDE for the ylide.

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Section: Introductionmentioning

confidence: 99%

Sulfur and Selenium Ylide Bond Enthalpies

et al. 2007

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“…For SNCT-900-1/1, the sulfur species can be assigned to the C-S-C moieties (164.0 eV for 2p 3/2 and 165.3 eV for 2p 1/2 of thiophene S) [12] and the nitrogen species exist as four configurations; that is, pyridinic N (398.20 AE 0.05 eV), pyrrollic N (400.60 AE 0.05 eV), graphitic N (401.35 AE 0.05 eV), and oxidized N species (403.70 AE 0.05 eV). [7d, 8a] The absence of NÀS bonds (397.0 eV) [13] implies that S and N are mostly isolated in SNCT. The N contents of the SNCT samples increase with increasing cysteine amount or with decreasing annealing temperature, in the range of 2.5-3.0 at %.…”

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confidence: 99%

Sulfur and Nitrogen Codoped Carbon Tubes as Bifunctional Metal‐Free Electrocatalysts for Oxygen Reduction and Hydrogen Evolution in Acidic Media

Sun

Jiang

et al. 2016

Chemistry A European J

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What is the most significant result of this study? Sulfur and nitrogen codoped carbon tubes present high electroca-talytic performance for both oxygen reduction and hydrogen evolution reactions in acidic media. This is the first example of abifunc-tional metal-free electrocatalyst for oxygen reduction and hydrogen evolution, suggesting the prospect of technological combination of fuel cells with water electrolysis for clean energy utilization. What was the inspiration for this cover design? When we were invited to submit acover for consideration, the first thought is how to show the main features of the sulfur and nitrogen codoped carbon-based metal-free electrocatalyst: high-performance and bifunctional arising from the synergetic effect of sulfur and nitrogen dopants. Considering that this electrocatalyst can accelerate the oxygen reduction reaction to produce water in proton exchange membrane fuel cells and catalyze the hydrogen evolution reaction to split water in electrolytic cells, we depicted af uel cell and an electrolytic cell in the water with plentiful bubbles , and the cells could be technologically combined by the mutual electrocatalyst. What other topics are you working on at the moment? Beside our research on the development of non-precious metal electrocatalysts for oxygen reduction and hydrogen evolution, we are also active in exploring high-performance electrode materials for electrochemical energy storage. We focus on the rational design of mesostructured carbon-based and metal oxide electrodes for supercapacitors, lithium-ion batteries, and lithium-air batteries. Invited for the cover of this issue is the group of Qiang Wu and Zheng Hu at Nanjing University.T he image depicts sulfur and nitrogen codoped carbon tubesasbifunctional metal-freeelectrocatalysts for oxygen reduction and hydrogen evolution in acidic media. Read the full text of the article at

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“…The absence of N-S bonds (ca. 397.0 eV) further implies that S and N are mostly isolated in hSNCNC [42,58] . These compositions and status of nitrogen species lead to different chemical/electronic environments for neighboring carbon atoms and hence different electrocatalytic activities.…”

Section: Resultsmentioning

confidence: 90%