Abstract
The electronic and molecular structures and the relative stabilities of organic peracids X=C(R)-COOH and their cyclic tautomers, dioxiranes
, with R = Me, CF3; X = O, NH, were studied using the ab initio Hartree-Fock method and the density functional theory (B3LYP version) as well as at the MP2-MP4 Møller-Plesset levels of perturbation theory. Geometry optimization was performed by the UHF and B3LYP methods with the 6-31G** basis set and at the MP2/cc-pvtz level of theory. The acyclic form of the peracid is more stable than the cyclic dioxirane form irrespective of the nature of the substituent. The energy difference between these tautomers increases as the CF3 and NH groups are replaced by Me and O, respectively. Parameters of the activation barrier to tautomeric conversion increase in parallel with enhancement of the electron-accepting properties of both substituents. The transition state of tautomeric interconversion, which is topologically similar to the acyclic structure of the carbonyl oxide derivative R(HX)C=O+-O−, was found and characterized taking peroxyacetic acid as an example. The characteristic features of the transition state are an intramolecular “multicenter” H-bond and the charge distribution that is inconsistent with the canonical structure mentioned above. An appropriate reaction coordinate for the transformation of the quasi-tetrahedral dioxirane structure into a planar peroxyacetic acid structure is provided by the dihedral angle. Deprotonated anionic systems are characterized by much smaller differences between the relative stabilities of the open and closed forms of isomers and by much lower activation barriers to isomeric conversions.
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References
Catalytic Oxidations with Hydrogen Peroxide as Oxidant, Ed. G. Strukul, Kluwer Academic Publishers, Dordrecht, 1992.
I. I. Vol’nov, Peroksokompleksy vanadiya, niobiya, tantala [Peroxo Complexes of Vanadium, Niobium, and Tantalum], Nauka, Moscow, 1987 (in Russian).
D. V. Kazakov, A. I. Voloshin, V. P. Kazakov, V. V. Shereshovets, and N. I. Kabal’nov, Khimiya i hemilyuminestsentsiya dioksiranov [Chemistry and Chemiluminescence of Dioxiranes], Nauka, Moscow, 1999 (in Russian).
Ya. K. Syrkin and I. I. Moiseev, Usp. Khim., 1960, 29, 425 [Russ. Chem. Rev., 1960, 29, No. 4 (Engl. Transl.)].
J. O. Edwards and R. Curci, in Catalitic Oxidation with Hydrogen Peroxide as Oxidant, Ed. G. Strukul, Kluwer Academic Publishers, Dordrecht, 1992.
P. D. Bartlett, Record Chem. Progr., 1950, 11, 47.
H. Mimoun, Angew. Chem., Int. Ed. Engl., 1982, 21, 734.
I. I. Moiseev, J. Molec. Catal., A: Chemical., 1997, 127, 1.
R. D. Bach and M.-D. Su, J. Am. Chem. Soc., 1994, 114, 10105.
J. A. Pople, K. Raghavachari, M. Frisch, J. S. Binkley, and P. v. R. Schleyer, J. Am. Chem. Soc., 1983, 105, 6389.
C. Meredith, T. P. Hamilton, and H. F. Schaeffer, III, J. Chem. Phys., 1992, 96, 9250.
W. Adam, R. Curci, and J. O. Edwards, Accounts Chem. Res., 1989, 22, 205.
R. D. Bach, A. L. Owensby, J. L. Andres, H. B. Schlegel, and J. J. W. McDouall, J. Am. Chem. Soc., 1992, 114, 7207.
D. Cremer, J. Gauss, E. Kraka, J. F. Stanton, and R. J. Bartlett, J. Chem. Phys. Lett., 1993, 209, 547
E. Kraka, Z. Konkoli, D. Cremer, J. Fowler, and H. F. Schaefer, III, J. Am. Chem. Soc., 1996, 118, 10595.
C. Selzuki and V. Aviyente, Theochem., 1999, 492, 165.
C. Selzuki and V. J. Aviyente, Molecular Modeling, 2001, 7, 70.
X.-Y. Wu, X. She, and Y. Shi, J. Am. Chem. Soc., 2002, 124, 8792.
I. V. Yudanov, P. Gisdakis, C. Di Valentin, and N. Rosch, Eur. J. Inorg. Chem., 1999, 12, 2135
A. F. Shestakov and N. S. Emel’yanova, Izv. Akad. Nauk, Ser. Khim., 2003, 1375 [A. F. Shestakov, N. S. Emel’yanova, Russ. Chem. Bull., Int. Ed., 2003, 52, 1455].
R. D. Bach, J. E. Winter, and J. J. W. McDouall, J. Am. Chem. Soc., 1995, 117, 8586.
S. Yamabe, C. Kondou, and T. Minato, J. Org. Chem., 1996, 61, 616.
R. D. Bach, M. N. Glukhovtsev, C. Gonzalez, M. Marquez, C. M. Estevez, A. Baboul, and H. B. Schlegel, J. Phys. Chem., 1997, 101, 6092.
S. L. Khursan and V. L. Antonovsky, Izv. Akad. Nauk, Ser. Khim., 2003, 1809 [Russ. Chem. Bull., Int. Ed., 2003, 52, 1908].
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. G. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, and J. A. Pople, GAUSSIAN, Gaussian, Inc., Pittsburgh (PA), 1998.
N. Feeder and W. Jones, Acta Crystallogr., Sect. C, 1994, 50, 1347.
N. Feeder and W. Jones, Acta Crystallogr., Sect. C, 1996, 52, 919, 1516, 2323.
R. D. Suenram and F. J. Lovas, J. Am. Chem. Soc., 1978, 100, 5117.
W. Sander, K. Schroeder, S. Muthusamy, A. Kirschfeld, W. Kappert, R. Boese, E. Kraka, C. Sosa, and D. Cremer, J. Am. Chem. Soc., 1997, 119, 7265.
I. B. Bersuker and V. Z. Polinger, Vibronnye vzaimodeistviya v molekulakh i kristallakh [Vibronic Interactions in Molecules and Crystals], Nauka, Moscow, 1983 (in Russian).
A. A. Levin and P. N. D’yachkov, Elektronnoe stroenie, struktura i prevrashcheniya geteroligandnykh molekul [Electronic Structure, Geometry, and Transformations of Heteroligand Molecules], Nauka, Moscow, 1990 (in Russian).
M. Ichikawa, Acta Crystallogr., Sect. B, 1978, 34, 2074.
W. Joswig, H. Fuess, and G. Ferraris, Acta Crystallogr., Sect. B, 1982, 38, 2798.
A. E. Read and P. v. R. Schleyer, J. Am. Chem. Soc., 1987, 109, 7362.
A. N. Lazarev, B. F. Shchegolev, M. A. Smirnov, and S. P. Dolin, Kvantovaya khimiya molekulyarnykh sistem i kristallokhimiya silikatov [Quantum Chemistry of Molecular Systems and Crystal Chemistry of Silicates], Nauka, Leningrad, 1988 (in Russian).
S. P. Dolin, Yu. P. Dikov, and V. I. Rekharskii, Geokhimiya, 1988, 7, 915 [Geochemistry, 1988, 7 (Engl. Transl.)].
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Dedicated to Academician A. L. Buchachenko on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1962–1972, September, 2005.
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Zubarev, D.Y., Filimonova, N.B., Timokhina, E.N. et al. Tautomerism of peroxyacetic acid derivatives: a quantum chemical study. Russ Chem Bull 54, 2023–2033 (2005). https://doi.org/10.1007/s11172-006-0074-9
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DOI: https://doi.org/10.1007/s11172-006-0074-9