Stable Ion Studies of Protonation and Oxidation of Polycyclic Arenes<sup>,</sup>

Laali, Kenneth K.

doi:10.1021/cr941175s

Cited by 52 publications

(56 citation statements)

References 95 publications

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“…Theoretical predictions are in accordance with NMR measurements of these persistent cations identified in superacid media. 33,35 Hence PA increments can be employed, if handled with due care, in predicting sites of electrophilic attack in substituted methylnaphthalenes. In particular, there should be a close linear relationship between the PAs estimated by the additivity rule and the basicity of these compounds.…”

Section: Resultsmentioning

confidence: 99%

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Proton affinity of substituted naphthalenes

Eckert‐Maksić¹,

Antol²,

Klessinger³

et al. 1999

J. Phys. Org. Chem.

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The absolute proton affinity (PA) of aromatic carbons of monosubstituted naphthalenes with CH 3 , OH, CHO, NO 2 and Cl substituents was calculated at the MP2(fc)/6-31G**//HF/6-31G* ZPVE(HF/6-31G*) level of theory. Increments corresponding to unsubstituted positions within the naphthalene skeleton were estimated. They can be used in estimating PAs of polysubstituted naphthalenes by using a simple additivity rule based on the independent substituent approximation (ISA). It is shown that increments are good indicators of the electrophilic substitution reactivity. The proton affinities of a large number of polysubstituted methylnaphthalenes was examined employing the additivity equation. It was found that the protonated forms, which exhibit the largest PAs, correspond to arenium ions observed by NMR spectroscopy in superacid media.

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Section: Resultsmentioning

confidence: 99%

“…Finally, we consider here the most stable protonated forms of methylated naphthalenes, which have been studied in superacid media by NMR spectroscopy. 35 Absolute proton affinities obtained by the additivity Eqn. (2) are given in Table 3.…”

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confidence: 99%

Proton affinity of substituted naphthalenes

Eckert‐Maksić¹,

Antol²,

Klessinger³

et al. 1999

J. Phys. Org. Chem.

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“…1325 There have been deep discussions on the stability of dicationic species of PAHs. 26 As an interesting example, Bettinger et al have discovered the fact that dications of higher linear acenes are formed more easily with growing size in sulfuric acid. 27 A computational analysis of anthracene concluded that the doubly charged system could be drawn with two Clar sextets.…”

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confidence: 99%

Studies on Pyrene and Perylene Derivatives upon Oxidation and Application to a Higher Analogue

Matsumoto

Suzuki

Hayashi

et al. 2017

Bulletin of the Chemical Society of Japan

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she was a researcher of PRESTO, JST, and then a group leader of CREST project (2010)(2011)(2012)(2013)(2014)(2015)(2016), JST, on "Construction of organic thin-film solar cells with innovative solutionprocessible organic materials". Her current research focuses on the development of functional organic materials including solution-processable molecular materials for organic electronics applications, large acenes and bottom-up synthesis of graphene nanoribbons. AbstractThe structure and electronic features of neutral and positively charged pyrene and perylene derivatives were explored. The radical cation of 1,3,6,8-tetraarylpyrene 1 was examined by ESR, UVvisNIR spectroscopy and theoretical calculations. The addition of 2 equiv of oxidant to 1 resulted in the formation of dication 1 2+. The single-crystal X-ray structure of 1 2+ proved that the aromatic part relocates from biphenyl unit to naphthyl unit upon 2e ¹ oxidation of 1. We have also investigated the oxidation processes of 3,9-diarylperylene 2 and 3,10-diarylperylene 3. The radical cations of 2•+ and 3 •+ showed ESR signals and the spin densities were proven to delocalize at 3,4,9,10-positions. In the case of doubly charged 3,9-diarylperylene, we could find the anthracene structure in the core, while the phenanthrene skeleton appeared in two-electron oxidized 3,10-diarylperylene. Finally we validated this phenomenon to apply for the higher analogue terrylene, discovering its large aromaticity relocation upon the 2e ¹ oxidation.

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“…There is increasing evidence that carcinogenic/mutagenic activity which ultimately leads to PAH-DNA adduct formation is initiated by electrophilic and/or oxidation chemistry involving PAH carbocations or radical cations [3±7]. Protonated PAHs have long been known in solution and have been characterized, in particular, by NMR [4]. A number of protonated PAHs are also known in the gas phase and have provided the corresponding proton anities.…”

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confidence: 99%

“…The PAHs themselves have been optimized at the HF/6-31G* level previously [21], but the results are repeated here for convenience. Semiempirical calculations are available for many of the protonated derivatives [4,22]. Total electronic energies (hartree) for these methods are listed in Table 1 for several PAHs and for the compounds protonated at the positions indicated by the number.…”

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confidence: 99%

An ab initio study of electrophilic aromatic substitution

Wang

Streitwieser

1999

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

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Proton anities are calculated at all reactive positions for the normal benzenoid hydrocarbons, benzene, naphthalene, phenanthrene and anthracene, a strained benzenoid hydrocarbon, biphenylene, and a nonalternant hydrocarbon,¯uoranthene, and the results are compared to experimental protodetritiation rates. Methods used include PM3 and Hartree-Fock calculations at the STO-3G, 3-21G*, 6-31G* and MP2//6-31G* levels. Generally good agreement is found between theory and experiment with 6-31G* giving the best correlations.

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Stable Ion Studies of Protonation and Oxidation of Polycyclic Arenes^,

Cited by 52 publications

References 95 publications

Proton affinity of substituted naphthalenes

Proton affinity of substituted naphthalenes

Studies on Pyrene and Perylene Derivatives upon Oxidation and Application to a Higher Analogue

An ab initio study of electrophilic aromatic substitution

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Stable Ion Studies of Protonation and Oxidation of Polycyclic Arenes,

Cited by 52 publications

References 95 publications

Proton affinity of substituted naphthalenes

Proton affinity of substituted naphthalenes

Studies on Pyrene and Perylene Derivatives upon Oxidation and Application to a Higher Analogue

An ab initio study of electrophilic aromatic substitution

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Stable Ion Studies of Protonation and Oxidation of Polycyclic Arenes^,