Ozonolysis of perfluorolefins
Russ. Chem. Bull., Int. Ed., Vol. 70, No. 1, January, 2021
139
12. M. Mashino, Y. Ninomiya, M. Kawasaki, T. J. Wallington,
M. D. Hurley, J. Phys. Chem. A, 2002, 104, 7255; DOI:
10.1021/jp000498r.
13. G. Acerboni, J. A. Beukes, N. R. Jensen, J. Hjorth, G. Myhre,
C. J. Nielsen, J. K. Sundet, Atmos. Environ., 2001, 35, 4113;
DOI: 10.1016/S1352-2310(01)00209-6.
14. A. V. Maiorov, B. E. Krisyuk, A. A. Popov, Khim. Fiz. [Chem.
Phys.], 2007, 26, 22 (in Russian).
15. B. E. Krisyuk, A. V. Maiorov, E. A. Mamin, V. A. Ovchinnikov,
A. A. Popov, Kinet. Catal., 2015, 56, 76; DOI: 10.1134/
s0023158415010085.
16. T. V. T. Mai, M. V. Duong, H. T. Nguyen, L. K. Huynh, Phys.
Chem. Chem. Phys., 2018, 20, 28059; DOI: 10.1039/
c8cp05386c.
17. A. V. Maiorov, B. E. Krisyuk, A. A. Popov, Russ. J. Phys.
Chem. B., 2008, 2, 707; DOI: 10.1134/s1990793108050084.
18. D. P. Kiryukhin, I. L. Ismoilov, I. M. Barkalov, Khim. Fiz.
[Chem. Phys.], 2003, 22, 123 (in Russian).
19. D. P. Kiryukhin, G. A. Kichigina, S. R. Allayarov, E. R.
Badamshina, High Energy Chem., 2019, 53, 228; DOI:
10.1134/S0018143919030081.
20. Chemcraft Graphical Software for Visualization of Quantum
21. M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert,
M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A.
Nguyen, S. J. Su, T. L. Windus, M. Dupuis, J. A. Montgomery,
J. Comput. Chem., 1993, 14, 1347; DOI:10.1002/jcc.540141112.
22. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone,
B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng,
J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda,
J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta,
F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin,
V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand,
K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar,
J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E.
Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo,
R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin,
R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin,
K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J.
Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B.
Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09,
Revision B.01, Gaussian, Inc., Wallingford CT, 2010; DOI:
10.1159/000348293.
Possible reaction routes via the concerted and non-
concerted addition mechanisms were examined by the
B2PLYP/aug-cc-pVDZ quantum chemical method. The
first channel has one symmetric TS for TFE and two TS
for HFP. The second channel has two TS for TFE and
four TS for HFP.
The calculated activation energy for the total reaction
rate constant (i.e., for the reaction via all parallel channels)
is 46 and 50 kJ mol–1 for TFE and HFP, respectively. The
calculated rate constant is 20—40 times lower than the
experimental value for both perfluorolefins, which is ex-
plained by the cage effect appeared in experiment.
It is shown for TFE that the nonconcerted addition is
the major channel at all temperatures. For HFP, both
channels are comparable, but at low temperature the
concerted addition channel prevails, and the fraction of
the reaction via the nonconcerted addition channel in-
creases with increasing temperature.
The calculation data for the activation energies and
reaction rate constants correspond to the experimentally
found values.
Primary ozonides obtained at the first step are initiators
of polymerization of diverse monomers.
This work was financially supported by the Institute of
Problems of Chemical Physics of the Russian Academy of
Sciences in the framework of state assignments No. 0089-
2019-0008 and 0089-2019-0005 (state registration
No. AAAA-A19-119041090087-4 and AAAA-
A19-119101690058-9).
References
1. R. Criegee, Ang. Chem. Int. Ed. Engl., 1975, 14, 745; DOI:
10.1002/anie.197507451.
2. R. Criegee, Ang. Chem., 1975, 87, 765; DOI:10.1002/
ange.19750872104.
3. W. B. DeMore, Int. J. Chem. Kinet., 1969, 1, 209; DOI:
10.1002/kin.550010207.
4. O. B. Gadzhiev, S. K. Ignatov, B. E. Krisyuk, A. V. Maiorov,
S. Gangopadhyay, A. E. Masunov, J. Phys. Chem. A, 2012,
116, 10420; DOI:10.1021/jp307738p.
5. E. T. Denisov, B. E. Krisyuk, Khim. Fiz. [Chem. Phys.], 2007,
26, 34 (in Russian).
gran/firefly/index.html.
6. A. V. Mayorov, B. E. Krisyuk, N. Sokolova, Comp. Theor.
Chem., 2020, 1186, 112904; DOI: 10.1016/j.comptc.
2020.112904.
7. S. D. Razumovskii, G. E. Zaikov, Ozon i ego reaktsii s organi-
cheskimi soedineniyami [Ozone and Its Reactions with Organic
Compounds], Nauka, Moscow, 1974, 322 pp. (in Russian).
8. T.Vrbaski, R. J. Cvetanovich, Can. J. Hem., 1960, 38, 1063.
9. J. Heicklen, J. Phys. Chem., 1966, 70, 477.
10. F. Gozzo, G. Camaggi, La Chim. Indast. (Milan), 1968,
50, 197.
24. S. K. Ignatov, Moltran v.2.5, Nizhny Novgorod, 2004—2015;
25. D. Cremer, J. Amer. Chem. Soc., 1981, 103, 3633.
26. S. D. Razumovskii, Khim. Fiz. [Chem. Phys.], 2000, 19, 58
(in Russian).
Received July 7, 2020;
in revised form August 10, 2020;
accepted October 2, 2020
11. A. I. Mezentsev, B. S. Karpov, V. A. Poluektov, Dokl. Akad. Nauk
SSSR [Proc. Acad. Sci. USSR], 1989, 306, 657 (in Russian).