Modeling Decomposition of N-Nitrosoamides in a Self-Assembled Capsule

Research output: Contribution to journal › Journal article › Research › peer-review

Standard

Modeling Decomposition of N-Nitrosoamides in a Self-Assembled Capsule. / Brea, Oriana; Daver, Henrik; Rebek, Julius; Himo, Fahmi.

In: Journal of Organic Chemistry, Vol. 84, No. 11, 07.06.2019, p. 7354-7361.

Research output: Contribution to journal › Journal article › Research › peer-review

Harvard

Brea, O, Daver, H, Rebek, J & Himo, F 2019, 'Modeling Decomposition of N-Nitrosoamides in a Self-Assembled Capsule', Journal of Organic Chemistry, vol. 84, no. 11, pp. 7354-7361. https://doi.org/10.1021/acs.joc.9b01034

APA

Brea, O., Daver, H., Rebek, J., & Himo, F. (2019). Modeling Decomposition of N-Nitrosoamides in a Self-Assembled Capsule. Journal of Organic Chemistry, 84(11), 7354-7361. https://doi.org/10.1021/acs.joc.9b01034

Vancouver

Brea O, Daver H, Rebek J, Himo F. Modeling Decomposition of N-Nitrosoamides in a Self-Assembled Capsule. Journal of Organic Chemistry. 2019 Jun 7;84(11):7354-7361. https://doi.org/10.1021/acs.joc.9b01034

Author

Brea, Oriana ; Daver, Henrik ; Rebek, Julius ; Himo, Fahmi. / Modeling Decomposition of N-Nitrosoamides in a Self-Assembled Capsule. In: Journal of Organic Chemistry. 2019 ; Vol. 84, No. 11. pp. 7354-7361.

Bibtex

@article{66b4d8412d034ac0881ac0688ba868b9,
title = "Modeling Decomposition of N-Nitrosoamides in a Self-Assembled Capsule",
abstract = "Density functional theory calculations are employed to investigate the mechanism and energies of the decomposition of N-nitrosoamides in the presence of a resorcinarene-based self-assembled nanocapsule. From experiments, it is known that confinement in the capsule inhibits the thermal decomposition of these compounds. N-Nitrosoamides with both aromatic and aliphatic substituents are considered here and the calculations show that, for both kinds, binding to the capsule leads to a significant increase in the energy barrier of the rate-determining step, the 1,3 N→O acyl transfer reaction. A distortion-interaction analysis is conducted to probe the reasons behind the inhibition of the reaction. In addition, we characterized hypothetical intermediates that might be involved in the formation of the decomposition products inside the capsule. Interestingly, it is found that the capsule stabilizes ion-pair species that are unstable in mesitylene solution. Finally, a possible explanation is proposed for the observed encapsulation of the decomposition product of only one of the substrates.",
author = "Oriana Brea and Henrik Daver and Julius Rebek and Fahmi Himo",
year = "2019",
month = jun,
day = "7",
doi = "10.1021/acs.joc.9b01034",
language = "English",
volume = "84",
pages = "7354--7361",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "11",

}

RIS

TY - JOUR

T1 - Modeling Decomposition of N-Nitrosoamides in a Self-Assembled Capsule

AU - Brea, Oriana

AU - Daver, Henrik

AU - Rebek, Julius

AU - Himo, Fahmi

PY - 2019/6/7

Y1 - 2019/6/7

N2 - Density functional theory calculations are employed to investigate the mechanism and energies of the decomposition of N-nitrosoamides in the presence of a resorcinarene-based self-assembled nanocapsule. From experiments, it is known that confinement in the capsule inhibits the thermal decomposition of these compounds. N-Nitrosoamides with both aromatic and aliphatic substituents are considered here and the calculations show that, for both kinds, binding to the capsule leads to a significant increase in the energy barrier of the rate-determining step, the 1,3 N→O acyl transfer reaction. A distortion-interaction analysis is conducted to probe the reasons behind the inhibition of the reaction. In addition, we characterized hypothetical intermediates that might be involved in the formation of the decomposition products inside the capsule. Interestingly, it is found that the capsule stabilizes ion-pair species that are unstable in mesitylene solution. Finally, a possible explanation is proposed for the observed encapsulation of the decomposition product of only one of the substrates.

AB - Density functional theory calculations are employed to investigate the mechanism and energies of the decomposition of N-nitrosoamides in the presence of a resorcinarene-based self-assembled nanocapsule. From experiments, it is known that confinement in the capsule inhibits the thermal decomposition of these compounds. N-Nitrosoamides with both aromatic and aliphatic substituents are considered here and the calculations show that, for both kinds, binding to the capsule leads to a significant increase in the energy barrier of the rate-determining step, the 1,3 N→O acyl transfer reaction. A distortion-interaction analysis is conducted to probe the reasons behind the inhibition of the reaction. In addition, we characterized hypothetical intermediates that might be involved in the formation of the decomposition products inside the capsule. Interestingly, it is found that the capsule stabilizes ion-pair species that are unstable in mesitylene solution. Finally, a possible explanation is proposed for the observed encapsulation of the decomposition product of only one of the substrates.

UR - http://www.scopus.com/inward/record.url?scp=85066963059&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.9b01034

DO - 10.1021/acs.joc.9b01034

M3 - Journal article

C2 - 31062978

AN - SCOPUS:85066963059

VL - 84

SP - 7354

EP - 7361

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 11

ER -

ID: 241045241