Hybrids from the π−π Stacking of Graphene Oxide and Aromatic Sulfonic Compounds for Improved Proton Conductivity

Shudo, Yuta; Karim, Mohammad Razaul; Ohtani, Ryo; Nakamura, Masaaki; Hayami, Shinya

doi:10.1002/celc.201701026

Cited by 31 publications

(26 citation statements)

References 12 publications

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“…At this stage, we are unsure if reductive elimination occurs via a binuclear process where both the enolate and the aryl group are on adjacent metals, or if they occur from an intermediate with both groups on the same metal. Regardless, formation of the arylated ketone intermediate (19) is confirmed by our isolation studies described above. Previously reported work by Ritter and Sanford also confirms that this type of Pd(III) dimer is active in cross coupling reactions under oxidative conditions.…”

supporting

confidence: 66%

“…This expeditious approach to naphthalene core structures is significant because naphthalenes have a variety of technological and pharmacological uses, 17 including as templates to construct carbon nanotubes 18 and as proton conducting solid electrolytes. 19 In addition to the synthetic value of this new transformation, it also provides an opportunity to investigate bimetallic cooperativity and its impact on catalysis, as monometallic palladium catalysts do not achieve the same levels of reactivity as complexes 4 and 5. Our catalyst optimization studies probed the impact of different Lewis acids, temperatures, ligands, and solvents on the reaction efficiency (Table 1).…”

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confidence: 99%

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Bimetallic Cooperativity with a 2-Phosphinoimidazole-Derived Pd(II) Dimer Enables Naphthalene Synthesis via dimeric Pd(III) Catalysis

Ence¹,

Nazari²,

Moreno³

et al. 2020

Preprint

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We report the synthesis of bimetallic Pd(I) and Pd(II) complexes scaffolded on bidentate 2-phosphinoimidazole ligands. These complexes display unique catalytic activity and enable the expeditious formation of 1,3-disubstituted naphthalenes via an unprecedented coupling of aryl iodides and methyl ketones in the presence of silver triflate. Excellent substrate scope for naphthalene formation is also demonstrated. Mechanistic studies suggest that the transformation proceeds via Pd-catalyzed arylation of a methyl ketone, followed by cyclization with a second equivalent of ketone. Importantly, this ketone arylation processes occurs under oxidizing conditions, suggesting involvement of higher oxidation state dimeric Pd catalysts. Based on experiments and DFT calculations, we propose a mechanism involving high oxidation state Pd(III) bimetallic catalysis. These new bimetallic complexes possess reactivity that is not seen with monometallic Pd catalysts and we confirm the importance of the palladium catalyst for both arylation and cyclization for naphthalene formation.

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confidence: 66%

mentioning

confidence: 99%

Bimetallic Cooperativity with a 2-Phosphinoimidazole-Derived Pd(II) Dimer Enables Naphthalene Synthesis via dimeric Pd(III) Catalysis

Ence¹,

Nazari²,

Moreno³

et al. 2020

Preprint

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show abstract

“…e adsorption energy for the phenyldiazonium cation is −45 kcal/mol, a value that is slightly higher (nearly −5 kcal/ mol) than the adsorption energy of nitrophenyldiazonium cation. is suggests that the interaction mode is mainly a π-π stacking one [23], so probably, the reason of the slightly lower adsorption energy for the nitrophenyl cation is the distortion of its planarity, decreasing its π stacking ability with the GOx surface.…”

Section: Resultsmentioning

confidence: 99%

Interactions between the Aryldiazonium Cations and Graphene Oxide: A DFT Study

Berisha

2019

Journal of Chemistry

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Understanding the grafting behavior of the aryldiazonium cations is of fundamental and also of practical importance for the vast number of applications that involve the use of modified graphene oxide (from simple adsorption process to electronic and photovoltaic applications). In this work, the mechanism of the adsorption and grafting of diazonium cations on the graphene oxide surface was investigated by the use of density functional theory. Two types of aryldiazonium cations, one bearing only phenyl ring and the other nitrophenyl, were selected as adsorbates/grafted moiety. By evaluating the adsorption energies at 7 different positions onto the graphene oxide both in the gaseous and solvent phase (using COSMO approach), the most probable adsorption sites were found. Moreover, the most stable adsorption sites were used to calculate and plot NCI (noncovalent interactions). The obtained results are important as they not only give molecular insights regarding the nature of the interaction and its dependence on the adsorption site of the graphene oxide surface but also on the activation energy for such a grafting reaction to take place, providing a mechanistic aspect to understand these grafting reactions.

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“…The adsorption energy for the phenyldiazonium cation is -45 kcal/mol, a value that is slightly higher (nearly -5 kcal/mol) than the adsorption energy of nitrophenyl diazonium cation. This suggests that the interaction mode is mainly a π-π stacking one [23], so probably the reason of the slightly lower adsorption energy for the nitrophenyl cation is the distortion of its planarity, decreasing its π stacking ability with the GOx surface. To asses correctly the interaction type [24], the NCI (Non-Covalent interaction) plot and the Reduced Density Gradient (RDG) vs. sign(λ)ρ were computed [25] for the highest adsorption site.…”

Section: Resultsmentioning

confidence: 99%

Interactions Between the Aryldiazonium Cations and Graphene Oxide – a DFT Study

Berisha¹

2019

Preprint

View full text Add to dashboard Cite

Understanding the grafting behavior of the aryldiazonium cations is of fundamental and also of practical importance for the vast number of applications that involve the use of modified Graphene oxide (from simple adsorption process to electronic and photovoltaic applications). In this work, the mechanism of the adsorption and grafting diazonium cations on the graphene oxide surface was investigated by the use of Density Functional Theory. Two types of aryldiazonium cations one bearing only phenyl ring and the other nitrophenyl were selected as adsorbates/grafted moiety. By evaluating the adsorption energies at 7 different positions onto the graphene oxide both in the gaseous and solvent phase (using COSMO approach) the most probable adsorption sites were found. Moreover, the most stable adsorption sites were used to calculate and plot NCI (Non-Covalent Interactions). The obtained results are important as they not only give molecular insights regarding the nature of the interaction and its dependence on the adsorption site of graphene oxide surface but also on the activation energy for such a grafting reaction to take place - providing a mechanistic aspect to understand these grafting reactions.

show abstract

Hybrids from the π−π Stacking of Graphene Oxide and Aromatic Sulfonic Compounds for Improved Proton Conductivity

Cited by 31 publications

References 12 publications

Bimetallic Cooperativity with a 2-Phosphinoimidazole-Derived Pd(II) Dimer Enables Naphthalene Synthesis via dimeric Pd(III) Catalysis

Bimetallic Cooperativity with a 2-Phosphinoimidazole-Derived Pd(II) Dimer Enables Naphthalene Synthesis via dimeric Pd(III) Catalysis

Interactions between the Aryldiazonium Cations and Graphene Oxide: A DFT Study

Interactions Between the Aryldiazonium Cations and Graphene Oxide – a DFT Study

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