Abstract
A kinetic model was developed for the reaction of ethylene oxidation to acetaldehyde by p-benzoquinone (Q) at 30 ℃ catalyzed by the cationic palladium(II) complexes in a binary acetonitrile—water solvent at a molar fraction of water of 0.67. The three-route mechanism was proposed that adequately describes all experimental dependences of the concentrations of consumed ethylene on time at various partial ethylene pressures and concentrations of palladium, perchloric acid, and Q. The time-dependent (a) palladium distribution between the intermediates and (b) ratio of the rates of steps of acetaldehyde oxidation via different routes were analyzed. The role of the PdII, PdI, and Pd0 complexes in the catalytic formation of olefins was discussed. The quantum chemical estimates of the composition of the coordination sphere for several intermediates and probabilities of some elementary steps in the reaction mechanism were obtained.
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References
A. Sen, Lai Ta-Wang, J. Am. Chem. Soc., 1981, 103, 4627.
A. Sen, Lai Ta-Wang, Organometallics, 1982, 1, 415.
Lai Ta-Wang, A. Sen, Organometallics, 1984, 3, 866.
L. S. Hegedus, T. A. Mulbern, H. Asada, J. Am. Chem. Soc., 1986, 108, 6224.
J. Tsuji, M. Minato, Tetrahedron Lett., 1987, 28, 3683.
J.-E. Backvall, R. B. Hopkins, Tetrahedron Lett., 1988, 29, 2885.
D. G. Miller, D. D. M. Wayner, J. Org. Chem., 1990, 55, 2924.
M. Scumov, E. Balbolov, Catal. Lett., 2000, 69, 103.
O. N. Temkin, L. G. Bruk, D. S. Zakharova, K. Yu. Odintsov, E. A. Katsman, I. V. Petrov, O. Yu. Istomina, Kinet. Catal., 2010, 51, 691.
D. S. Zakharova, A. N. Semenyako, O. A. Chertkova, A. V. Frolkova, E. A. Katsman, L. G. Bruk, O. N. Temkin, Tonkie Khim. Tekhnol. [Fine Chemical Technologies], 2015, 10, 77 (in Russian).
O. N. Temkin, D. S. Zakharova, O. A. Chertkova, A. S. Chelkin, L. G. Bruk, Russ. Chem. Bull., 2013, 62, 844.
I. V. Martynov, G. E. Efremov, O. N. Temkin, Russ. Chem. Bull., 2017, 66, 922.
B. J. Anderson, J. A. Keith, M. S. Sigman, J. Am. Chem. Soc., 2010, 132, 11872.
G. E. Efremov, E. A. Bovyrina, A. V. Podtyagina, I. V. Oshanina, O. N. Temkin, Kinet. Catal., 2019, 60, 52.
I. V. Martynov, G. E. Efremov, E. A. Bovyrina, E. A. Katsman, O. N. Temkin, Kinet. Catal., 2018, 59, 436.
D. N. Laikov, Chem. Phys. Lett., 1997, 281, 151.
D. N. Laikov, Yu. A. Ustynyuk, Russ. Chem. Bull., 2005, 54, 820.
J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865.
D. N. Laikov, Chem. Phys. Lett., 2005, 416, 116.
E. A. Katsman, A. S. Berenblyum, Paket programm dlya postroeniya i analiza kineticheskikh modelei i ego primenenie, MITKhT im. M. V. Lomonosova [Program Software for Construc tion and Analysis of Kinetic Models and Its Application, M. V. Lomonosov Moscow Institute of Fine Chemical Technologies], Moscow, 2010 (in Russian).
D. S. Zakharova, I. V. Martynov, V. M. Nosova, O. N. Temkin, Tonkie Khim. Tekhnol. [Fine Chemical Technologies], 2016, 11, No. 2, 57 (in Russian).
I. I. Moiseev, π-Kompleksy olefi nov v zhidkofaznom okislenii [π-Complexes of Olefi ns in Liquid-Phase Oxidation], Nauka, Moscow, 1970, 270 pp. (in Russian).
J. A. Keith, P. M. Henry, Angew. Chem., Int. Ed., 2009, 48, 9038.
O. N. Temkin, Kinet. Catal., 2014, 55, 172.
O. N. Temkin, L. G. Bruk, Oxidative Carbonylation — Homogeneous. Encyclopedia of Catalysis, Ed. I. T. Horvath, Wiley-Interscience, Hoboken, New Jersey, 2003, V. 5, 394 pp.
O. N. Temkin, L. G. Bruk, Kinet. Katal., 2003, 44, 661 [Kinet. Catal. (Engl. Transl.), 2003, 44].
O. N. Temkin, Homogeneous Catalysis with Metal Complexes. Kinetic Aspects and Mechanisms, Wiley, Chichester, UK, 2012.
K. I. Matveev, N. B. Shitova, E. G. Zhizhina, Kinet. Katal., 1976, 17, 893 [Kinet. Catal. (Engl. Transl.), 1976, 17].
E. G. Zhizhina, N. B. Shitova, K. I. Matveev, Kinet. Katal., 1981, 22, 1451 [Kinet. Catal. (Engl. Transl.), 1981, 22].
A. V. Kulik, L. G. Bruk, O. N. Temkin, V. R. Khabibulin, V. K. Belsky, V. E. Zavadnik, Mendeleev Commun., 2002, 12, 47.
H. Grennberg, A. Gogoll, J.-E. Backvall, Organometallics., 1993, 12, 1790.
B. V. Popp, S. S. Stahl, Top Organomet. Chem., 2007, 22, 149.
V. G. Gorskii, E. A. Katsman, F. D. Klebanova, A. A. Grigor'ev, Teor. Eksp. Chem., 1987, 23, 181.
P. E. M. Siegbahn, J. Phys. Chem., 1996, 100, 14672.
J. A. Keith, R. J. Nielsen, J. Oxgaard, W. A. Goddard, J. Am. Chem. Soc., 2007, 129, 12342.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1366–1375, July, 2019.
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Efremov, G.E., Bovyrina, E.A., Katsman, E.A. et al. Kinetic model of ethylene oxidation by p-benzoquinone in solutions of cationic palladium(ii) complexes in a binary acetonitrile—water solvent. Russ Chem Bull 68, 1366–1375 (2019). https://doi.org/10.1007/s11172-019-2563-7
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DOI: https://doi.org/10.1007/s11172-019-2563-7