NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines

Standard

NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines. / Cherkasov, Sergey; Parkhomenko, Dmitriy; Genaev, Alexander et al.

In: Molecules (Basel, Switzerland), Vol. 25, No. 21, 5080, 01.11.2020.

Research output: Contribution to journal › Article › peer-review

Harvard

Cherkasov, S, Parkhomenko, D, Genaev, A, Salnikov, G, Edeleva, M, Morozov, D, Rybalova, T, Kirilyuk, I, Marque, SRA & Bagryanskaya, E 2020, 'NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines', Molecules (Basel, Switzerland), vol. 25, no. 21, 5080. https://doi.org/10.3390/molecules25215080

APA

Cherkasov, S., Parkhomenko, D., Genaev, A., Salnikov, G., Edeleva, M., Morozov, D., Rybalova, T., Kirilyuk, I., Marque, S. R. A., & Bagryanskaya, E. (2020). NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines. Molecules (Basel, Switzerland), 25(21), [5080]. https://doi.org/10.3390/molecules25215080

Vancouver

Cherkasov S, Parkhomenko D, Genaev A, Salnikov G, Edeleva M, Morozov D et al. NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines. Molecules (Basel, Switzerland). 2020 Nov 1;25(21):5080. doi: 10.3390/molecules25215080

Author

Cherkasov, Sergey ; Parkhomenko, Dmitriy ; Genaev, Alexander et al. / NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines. In: Molecules (Basel, Switzerland). 2020 ; Vol. 25, No. 21.

BibTeX

@article{cea3f4850b9a491a837dce8b284154fd,

title = "NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines",

abstract = "Three alkoxyamines based on imidazoline radicals with a pyridine functional group-potential initiators of nitroxide-mediated, controlled radical polymerization-were synthesized. Electron Paramagnetic Resonance (EPR) measurements reveal biexponential kinetics for the thermolysis for diastereomeric alkoxyamines and monoexponential kinetics for an achiral alkoxyamine. For comparison, the thermolysis of all three alkoxyamines was studied by NMR in the presence of three different scavengers, namely tetramethylpiperidine-N-oxyl (TEMPO), thiophenol (PhSH), and β-mercaptoethanol (BME), and detailed analysis of products was performed. NMR differentiates between N-inversion, epimerization, and homolysis reactions. The choice of scavenger is crucial for making a reliable and accurate estimate of the true homolysis rate constant.",

keywords = "alkoxyamine, chirality, homolysis, imidazoline radical, kinetics, nitrogen inversion, nitroxide, nitroxide mediated polymerization, scavenger, stereoisomerization, MODEL ALKOXYAMINES, LIMITATIONS, NITROXIDES, DECOMPOSITION, IMIDAZOLINE, CONTROL AGENTS, N-O, SYSTEMS, RADICAL POLYMERIZATION, C-ON BOND",

author = "Sergey Cherkasov and Dmitriy Parkhomenko and Alexander Genaev and Georgii Salnikov and Mariya Edeleva and Denis Morozov and Tatyana Rybalova and Igor Kirilyuk and Marque, {Sylvain R.A.} and Elena Bagryanskaya",

note = "Publisher Copyright: {\textcopyright} 2020 by the authors. Licensee MDPI, Basel, Switzerland.",

year = "2020",

month = nov,

day = "1",

doi = "10.3390/molecules25215080",

language = "English",

volume = "25",

journal = "Molecules",

issn = "1420-3049",

publisher = "Multidisciplinary Digital Publishing Institute (MDPI)",

number = "21",

}

RIS

TY - JOUR

T1 - NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines

AU - Cherkasov, Sergey

AU - Parkhomenko, Dmitriy

AU - Genaev, Alexander

AU - Salnikov, Georgii

AU - Edeleva, Mariya

AU - Morozov, Denis

AU - Rybalova, Tatyana

AU - Kirilyuk, Igor

AU - Marque, Sylvain R.A.

AU - Bagryanskaya, Elena

PY - 2020/11/1

Y1 - 2020/11/1

N2 - Three alkoxyamines based on imidazoline radicals with a pyridine functional group-potential initiators of nitroxide-mediated, controlled radical polymerization-were synthesized. Electron Paramagnetic Resonance (EPR) measurements reveal biexponential kinetics for the thermolysis for diastereomeric alkoxyamines and monoexponential kinetics for an achiral alkoxyamine. For comparison, the thermolysis of all three alkoxyamines was studied by NMR in the presence of three different scavengers, namely tetramethylpiperidine-N-oxyl (TEMPO), thiophenol (PhSH), and β-mercaptoethanol (BME), and detailed analysis of products was performed. NMR differentiates between N-inversion, epimerization, and homolysis reactions. The choice of scavenger is crucial for making a reliable and accurate estimate of the true homolysis rate constant.

AB - Three alkoxyamines based on imidazoline radicals with a pyridine functional group-potential initiators of nitroxide-mediated, controlled radical polymerization-were synthesized. Electron Paramagnetic Resonance (EPR) measurements reveal biexponential kinetics for the thermolysis for diastereomeric alkoxyamines and monoexponential kinetics for an achiral alkoxyamine. For comparison, the thermolysis of all three alkoxyamines was studied by NMR in the presence of three different scavengers, namely tetramethylpiperidine-N-oxyl (TEMPO), thiophenol (PhSH), and β-mercaptoethanol (BME), and detailed analysis of products was performed. NMR differentiates between N-inversion, epimerization, and homolysis reactions. The choice of scavenger is crucial for making a reliable and accurate estimate of the true homolysis rate constant.

KW - alkoxyamine

KW - chirality

KW - homolysis

KW - imidazoline radical

KW - kinetics

KW - nitrogen inversion

KW - nitroxide

KW - nitroxide mediated polymerization

KW - scavenger

KW - stereoisomerization

KW - MODEL ALKOXYAMINES

KW - LIMITATIONS

KW - NITROXIDES

KW - DECOMPOSITION

KW - IMIDAZOLINE

KW - CONTROL AGENTS

KW - N-O

KW - SYSTEMS

KW - RADICAL POLYMERIZATION

KW - C-ON BOND

UR - http://www.scopus.com/inward/record.url?scp=85095391577&partnerID=8YFLogxK

U2 - 10.3390/molecules25215080

DO - 10.3390/molecules25215080

M3 - Article

C2 - 33139669

AN - SCOPUS:85095391577

VL - 25

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 21

M1 - 5080

ER -

ID: 25864371