Theoretical Study of Remote Substituent Effects on X–H(X=CH<sub>2</sub>, NH, O) Bond Dissociation Energies of Azulene

Yu, Yi; Fu, Yao; Liu, Lei; Guo, Qi

doi:10.1002/cjoc.200790162

Cited by 9 publications

(4 citation statements)

References 53 publications

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“…The Hammett-type analysis ,− can provide us with further implications on the effect of the R 1 group as well as the changing patterns of C–O BDEs in the substituted methanephosphates/methanesulfonates. The Brown-Okamoto substituent constants σ p + mainly based on the solvolysis of substituted t -cumyl chlorides are also listed in the table .…”

Section: Resultsmentioning

confidence: 99%

Homolytic C–O Cleavage in Phosphates and Sulfonates

2015

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The C-O homolytic bond dissociation enthalpies(BDEs) were calculated by high-level ab initio including G4, G3B3, G3, CBS-QB3 and a series of density function theory (DFT) methods. It is found that the wB97 method gave the most reliable C-O BDEs and the root-mean-square deviation (RMSD) is 7.6 kJ/mol. Therefore, the C(sp(2))-O BDE predictions and the substituent effects of alkenyl phosphates/sulfonates and aryl phosphates/sulfonates were investigated in detail by using the wB97 method. Interestingly, there exist different substituent effects in α- and β-substituted alkenyl phosphates/sulfonates. Excellent linear relationships between the C-O BDEs of β-substituted alkenyl phosphates/sulfonates with substituent constant σp(+) were found. In addition, the NBO analysis further disclosed the essence of the substituent effects on C-O BDEs.

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Section: Resultsmentioning

confidence: 99%

Homolytic C–O Cleavage in Phosphates and Sulfonates

2015

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“…(ii) Fe 2 O 3 @N‐CNFs coupled with Cl − capturing NiCo LDH@N‐CNFs showed SAC/ASAR as high as 114.97 mg g −1 /~5.75 mg g −1 min −1 in 500 mg L −1 NaCl solution at 1.2 V [191] . (iii) Cu@Cu 2 O/C‐1100//AC HCDI device showed an excellent SAC of 86.3 mg g −1 @ 0.02 A g −1 [192] . Here again, an excellent desalination performance is noticeable when the TMOs containing other Faradaic electrodes are applied in specific cell architecture or with the unconventional Cl − capturing anode (Table S2).…”

Section: Compositing/heterostructuring Of the Mxene For CDI Applicati...mentioning

confidence: 96%

MXene‐Based Capacitive Deionization–Strong Competitor Among Faradaic Electrode Systems: Current Status and Future Perspectives

Dubey

2023

ChemistrySelect

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Capacitive deionization (CDI) of brackish water is emerging as a sustainable and energy efficient desalination processes to mitigate the excessive demand of freshwater. Despite that the porous carbon is prime choice in the conventional CDI; its electrostatic interaction‐based limited salt adsorption capacity (SAC, up to 25 mg g−1) has driven the research interest to explore various Faradaic electrodes for attaining maximum SAC (>100 mg g−1) in supplementation with the other desalination metrics. MXene is one of the newly discovered intercalation‐type pseudocapacitive nanostructures, which promised an excellent desalination performance due to its intriguing properties, such as tuneable interlayer spacing, high electrical conductivity, hydrophilicity, and structural integrity. Furthermore, its compositing/heterostructuring with other electro‐active components significantly improves the desalination activity. This article provides a systematic overview of the MXene‐based electrodes utilized in CDI along with the one‐to‐one comparison with other Faradaic systems. Materials design, structure, cell architecture, desalination metrics‐based performance evaluation, and underlying driving forces behind the salty ions removal activity are the main emphasis of discussion to realize MXene‐based efficient CDI desalination. Lastly, the key issues and perspectives of MXene‐based electrode systems are put forward towards new developments and real time implication.

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“…The strong electron-donating ability of − NH 2 and the high-lying occupied orbitals which can repel the π electrons of the conjugated system lead to the weakness of the C−H bond. [50] When the EDG − N(CH 3 ) 2 is located at the β-position, the C−H BDE is the largest. Apart from the electron-donating ability, the strong conjugation effect of − N(CH 3 ) 2 perhaps make the C−H BDE larger.…”

Section: The Substituent Effects On C−h Bdes In Sulfur-containing Fusmentioning

confidence: 98%

A comparison of the C‒H bond dissociation enthalpies of sulfur-containing fused heterocyclic compounds to the C‒H bond dissociation enthalpies in other heterocycles

Wang

Zheng

2015

Journal of Sulfur Chemistry

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The C−H bond dissociation enthalpies (BDEs) of 26 N, O, S-containing mono-heterocyclic compounds were assessed by the composite high-level ab initio methods G4 and CBS-QB3. In addition, the C−H BDEs of 32 heterocyclic compounds were evaluated by 13 density functional theory methods. The BMK method showed the lowest root mean square error of 7.2 kJ/mol and the correlation coefficient (R 2 ) was 0.9874 after being compared with the experimental values. Subsequently, we used this method to study the C−H BDE values of the different positions as well as the substituent effects on benzene and heterocycles in sulfur-containing fused heterocyclic compounds. Both the natural charge distributions of benzo[b]thiophene and benzothiazole and natural spin densities of benzo[b]thiophene derivative radicals were conducted by NBO analysis for further understanding the essence of the C−H bond. 0 5 10 15 20 25 30 35 -80 -60 -40 -20 0 20 40 60 80 BMK KMLYP MPW1KCIS O3LYP PBE1PBE TPSS1KCIS M05 MPWB1K M06-L MPWLYPW WB97X B3LYP M06-2X BDE(Theor.)-BDE(Exp.)(kJ/mol) C-H bond S CN Br 2 (3 equiv),solvent r.t.,18h S CN Br + S CN Br 4 6 S CN + S CN major Br 5 Br 7 minor Scheme 1. Regioselectivity studies on bromination.

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Theoretical Study of Remote Substituent Effects on X–H(X=CH₂, NH, O) Bond Dissociation Energies of Azulene

Cited by 9 publications

References 53 publications

Homolytic C–O Cleavage in Phosphates and Sulfonates

Homolytic C–O Cleavage in Phosphates and Sulfonates

MXene‐Based Capacitive Deionization–Strong Competitor Among Faradaic Electrode Systems: Current Status and Future Perspectives

A comparison of the C‒H bond dissociation enthalpies of sulfur-containing fused heterocyclic compounds to the C‒H bond dissociation enthalpies in other heterocycles

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Theoretical Study of Remote Substituent Effects on X–H(X=CH2, NH, O) Bond Dissociation Energies of Azulene

Cited by 9 publications

References 53 publications

Homolytic C–O Cleavage in Phosphates and Sulfonates

Homolytic C–O Cleavage in Phosphates and Sulfonates

MXene‐Based Capacitive Deionization–Strong Competitor Among Faradaic Electrode Systems: Current Status and Future Perspectives

A comparison of the C‒H bond dissociation enthalpies of sulfur-containing fused heterocyclic compounds to the C‒H bond dissociation enthalpies in other heterocycles

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Theoretical Study of Remote Substituent Effects on X–H(X=CH₂, NH, O) Bond Dissociation Energies of Azulene