The formation of highly oxidized multifunctional products in the ozonolysis of cyclohexene

Matti P. Rissanen; Theo Kurtén; Mikko Sipilä; Joel A. Thornton; Juha Kangasluoma; Nina Sarnela; Heikki Junninen; Solvejg Jørgensen; Simon Schallhart; Maija K. Kajos; Risto Taipale; Monika Springer; Thomas F. Mentel; Taina Ruuskanen; Tuukka Petäjä; Douglas R. Worsnop; Henrik Grum Kjærgaard; Mikael Ehn

doi:10.1021/ja507146s

The formation of highly oxidized multifunctional products in the ozonolysis of cyclohexene

Matti P. Rissanen^*, Theo Kurtén, Mikko Sipilä, Joel A. Thornton, Juha Kangasluoma, Nina Sarnela, Heikki Junninen, Solvejg Jørgensen, Simon Schallhart, Maija K. Kajos, Risto Taipale, Monika Springer, Thomas F. Mentel, Taina Ruuskanen, Tuukka Petäjä, Douglas R. Worsnop, Henrik Grum Kjærgaard, Mikael Ehn

^*Corresponding author for this work

Department of Chemistry

156 Citations (Scopus)

Abstract

The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C₆H₁₀) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO₃ ^-)-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO₂) isomerization through intramolecular hydrogen shift reactions, followed by sequential O₂ addition steps, that is, RO₂ autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the formation of highly oxidized monomer species and is observed to lead to peroxides, potentially diacyl peroxides. The molar yield of these highly oxidized products (having O/C > 1 in monomers and O/C > 0.55 in dimers) from cyclohexene ozonolysis was determined as (4.5 ± 3.8)%. Fully deuterated cyclohexene and cis-6-nonenal ozonolysis, as well as the influence of water addition to the system (either H₂O or D₂O), were also investigated in order to strengthen the arguments on the proposed mechanism. Deuterated cyclohexene ozonolysis resulted in a less oxidized product distribution with a lower yield of highly oxygenated products and cis-6-nonenal ozonolysis generated the same monomer product distribution, consistent with the proposed mechanism and in agreement with quantum chemical modeling.

Original language	English
Journal	Journal of the American Chemical Society
Volume	136
Issue number	44
Pages (from-to)	15596-15606
Number of pages	11
ISSN	0002-7863
DOIs	https://doi.org/10.1021/ja507146s
Publication status	Published - 2014

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10.1021/ja507146s

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Rissanen, M. P., Kurtén, T., Sipilä, M., Thornton, J. A., Kangasluoma, J., Sarnela, N., Junninen, H., Jørgensen, S., Schallhart, S., Kajos, M. K., Taipale, R., Springer, M., Mentel, T. F., Ruuskanen, T., Petäjä, T., Worsnop, D. R., Kjærgaard, H. G., & Ehn, M. (2014). The formation of highly oxidized multifunctional products in the ozonolysis of cyclohexene. Journal of the American Chemical Society, 136(44), 15596-15606. https://doi.org/10.1021/ja507146s

Rissanen, MP, Kurtén, T, Sipilä, M, Thornton, JA, Kangasluoma, J, Sarnela, N, Junninen, H, Jørgensen, S, Schallhart, S, Kajos, MK, Taipale, R, Springer, M, Mentel, TF, Ruuskanen, T, Petäjä, T, Worsnop, DR, Kjærgaard, HG & Ehn, M 2014, 'The formation of highly oxidized multifunctional products in the ozonolysis of cyclohexene', Journal of the American Chemical Society, vol. 136, no. 44, pp. 15596-15606. https://doi.org/10.1021/ja507146s

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title = "The formation of highly oxidized multifunctional products in the ozonolysis of cyclohexene",

abstract = "The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3 -)-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps, that is, RO2 autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the formation of highly oxidized monomer species and is observed to lead to peroxides, potentially diacyl peroxides. The molar yield of these highly oxidized products (having O/C > 1 in monomers and O/C > 0.55 in dimers) from cyclohexene ozonolysis was determined as (4.5 ± 3.8)%. Fully deuterated cyclohexene and cis-6-nonenal ozonolysis, as well as the influence of water addition to the system (either H2O or D2O), were also investigated in order to strengthen the arguments on the proposed mechanism. Deuterated cyclohexene ozonolysis resulted in a less oxidized product distribution with a lower yield of highly oxygenated products and cis-6-nonenal ozonolysis generated the same monomer product distribution, consistent with the proposed mechanism and in agreement with quantum chemical modeling.",

author = "Rissanen, {Matti P.} and Theo Kurt{\'e}n and Mikko Sipil{\"a} and Thornton, {Joel A.} and Juha Kangasluoma and Nina Sarnela and Heikki Junninen and Solvejg J{\o}rgensen and Simon Schallhart and Kajos, {Maija K.} and Risto Taipale and Monika Springer and Mentel, {Thomas F.} and Taina Ruuskanen and Tuukka Pet{\"a}j{\"a} and Worsnop, {Douglas R.} and Kj{\ae}rgaard, {Henrik Grum} and Mikael Ehn",

year = "2014",

doi = "10.1021/ja507146s",

language = "English",

volume = "136",

pages = "15596--15606",

journal = "Journal of the American Chemical Society",

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TY - JOUR

T1 - The formation of highly oxidized multifunctional products in the ozonolysis of cyclohexene

AU - Rissanen, Matti P.

AU - Kurtén, Theo

AU - Sipilä, Mikko

AU - Thornton, Joel A.

AU - Kangasluoma, Juha

AU - Sarnela, Nina

AU - Junninen, Heikki

AU - Jørgensen, Solvejg

AU - Schallhart, Simon

AU - Kajos, Maija K.

AU - Taipale, Risto

AU - Springer, Monika

AU - Mentel, Thomas F.

AU - Ruuskanen, Taina

AU - Petäjä, Tuukka

AU - Worsnop, Douglas R.

AU - Kjærgaard, Henrik Grum

AU - Ehn, Mikael

PY - 2014

Y1 - 2014

N2 - The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3 -)-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps, that is, RO2 autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the formation of highly oxidized monomer species and is observed to lead to peroxides, potentially diacyl peroxides. The molar yield of these highly oxidized products (having O/C > 1 in monomers and O/C > 0.55 in dimers) from cyclohexene ozonolysis was determined as (4.5 ± 3.8)%. Fully deuterated cyclohexene and cis-6-nonenal ozonolysis, as well as the influence of water addition to the system (either H2O or D2O), were also investigated in order to strengthen the arguments on the proposed mechanism. Deuterated cyclohexene ozonolysis resulted in a less oxidized product distribution with a lower yield of highly oxygenated products and cis-6-nonenal ozonolysis generated the same monomer product distribution, consistent with the proposed mechanism and in agreement with quantum chemical modeling.

AB - The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3 -)-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps, that is, RO2 autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the formation of highly oxidized monomer species and is observed to lead to peroxides, potentially diacyl peroxides. The molar yield of these highly oxidized products (having O/C > 1 in monomers and O/C > 0.55 in dimers) from cyclohexene ozonolysis was determined as (4.5 ± 3.8)%. Fully deuterated cyclohexene and cis-6-nonenal ozonolysis, as well as the influence of water addition to the system (either H2O or D2O), were also investigated in order to strengthen the arguments on the proposed mechanism. Deuterated cyclohexene ozonolysis resulted in a less oxidized product distribution with a lower yield of highly oxygenated products and cis-6-nonenal ozonolysis generated the same monomer product distribution, consistent with the proposed mechanism and in agreement with quantum chemical modeling.

U2 - 10.1021/ja507146s

DO - 10.1021/ja507146s

M3 - Journal article

C2 - 25283472

AN - SCOPUS:84908638566

SN - 0002-7863

VL - 136

SP - 15596

EP - 15606

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 44

ER -

The formation of highly oxidized multifunctional products in the ozonolysis of cyclohexene

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