Abstract
The kinetics of the reactions of hydrogen atom abstraction from the C–H bonds of substrates of different structures by phthalimide-N-oxyl radicals is studied. The rate constants of this reaction are measured and the kinetic isotope effects are determined. It is shown that in addition to the thermodynamic factor, Coulomb forces and donor–acceptor interactions affect the reaction between phthalimide-N-oxyl radicals and substrate molecules, altering the shape of the transition state. This favors the tunneling of hydrogen atoms and leads to a substantial reduction in the activation energy of the process.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
E. T. Denisov, Russ. Chem. Rev. 66, 859 (1997).
W. Lai, Ch. Li, H. Chen, and S. Shaik, Angew. Chem., Int. Ed. Engl. 51, 2 (2012).
I. A. Opeida, Yu. E. Litvinov, O. V. Kushch, et al., Zh. Fiz. Khim. 88, 936 (2014).
Y. Ishii, S. Sakaguchi, and T. Iwahama, Adv. Synth. Catal. 343, 393 (2001).
N. Koshino, Y. Cai, and J. H. Espenson, J. Phys. Chem. A 107, 4262 (2003).
Y. Ishii and S. Sakaguchi, Catal. Surv. Jpn., No. 3, 27 (1999).
G. N. Koshel, E. V. Smirnova, E. A. Kurganova, et al., Catal. Ind. 4, 96 (2012).
I. A. Opeida, A. L. Plekhov, O. V. Kushch, and A. G. Matvienko, Russ. J. Phys. Chem. A 85, 1119 (2011).
K. Kasperczyk, B. Orlinska, and J. Zawadiak, Cent. Eur. J. Chem. 12, 1176 (2014).
F. Recupero and C. Punta, Chem. Rev. 107, 3800 (2007).
E. B. Merkushev and M. S. Shvartsberg, Organoiodine Compounds and Syntheses Based on Them (Tomsk. Univ., Tomsk, 1978) [in Russian].
M. P. Schwartz, R. J. Halter, R. J. McMahon, and R. J. Hamers, J. Phys. Chem. B 107, 224 (2003).
Yu-Ran Luo, Comprehensive Handbook of Chemical Bond Energies (CRC, New York, 2007).
Z. Alfassi, Peroxyl Radicals: The Chemistry of Free Radicals (Wiley, Chichester, 1997).
I. A. Opeida, Neftekhim. 26, 745 (1986).
R. Amorati, M. Lucarini, M. Mugnaini, et al., Org. Chem. 68, 1747 (2003).
N. Koshino, B. Saha, and J. H. Espenson, Org. Chem. 68, 9364 (2003).
E. T. Denisov, Russ. Chem. Rev. 42, 157 (1973).
T. Bredow and K. Jug, Theor. Chem. Acc. 113, 1 (2005).
K. W. Sattelmeyer, J. Tirado-Rives, and W. L. Jorgensen, J. Phys. Chem. A 110, 13551 (2006).
I. A. Opeida, V. I. Timokhin, and V. F. Galat, Teor. Eksp. Khim. 14, 554 (1978).
T. G. Denisova and E. T. Denisov, Kinet. Catal. 45, 301 (2004).
E. Baciocchi, M. F. Gerinni, and O. Lanzalunga, J. Org. Chem. 69, 8963 (2004).
C. Annunziantini, M. F. Gerinni, O. Lanzalunga, and M. Lucarini, J. Org. Chem. 69, 3431 (2004).
L. Melander and W. Saunders, Reaction Rates of Isotopic Molecules (Wiley, New York, 1980).
Y. H. Kim and M. M. Kreevoy, J. Am. Chem. Soc. 114, 7116 (1992).
W. P. Jencks, Catalysis in Chemistry and Enzymology, McGraw-Hill Series in Advanced Chemistry (McGraw-Hill, New York, 1969) [in Russian].
V. Malatesta and K. U. Ingold, J. Am. Chem. Soc. 103, 3094 (1981).
T. Doba and K. U. Ingold, J. Am. Chem. Soc. 106, 3958 (1984).
H. Muchalski, A. J. Levonyak, L. Xu, et al., J. Am. Chem. Soc. 137, 94 (2015).
L. I. Krishtalik, Biochim. Biophys. Acta: Bioenerget. 1458, 6 (2000).
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © I.A. Opeida, Yu.E. Litvinov, O.V. Kushch, M.A. Kompanets, A.N. Shendrik, A.G. Matvienko, A.A. Novokhatko, 2016, published in Zhurnal Fizicheskoi Khimii, 2016, Vol. 90, No. 11, pp. 1618–1625.
Rights and permissions
About this article
Cite this article
Opeida, I.A., Litvinov, Y.E., Kushch, O.V. et al. Rate constants and isotope effects for the reaction of H-atom abstraction from RH substrates by PINO radicals. Russ. J. Phys. Chem. 90, 2142–2149 (2016). https://doi.org/10.1134/S0036024416110194
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0036024416110194