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Pathways of the reactions of nucleophilic addition of H2O and HF molecules to formaldehyde in the gas phase and in the complex with formic acid:ab initio calculations

  • Physical Chemistry
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Abstract

The gradient pathways of the reactions of nucleophilic addition of H2O and HF molecules to formaldehyde in the gas phase and in the XH…H2CO…HC(O)OH complex (X=OH, F) were calculated by theab initio RHF/6-31G**, MP2(fc)/6-31G**, and MP2(full)/6-311++G** methods. Both reactions proceed concertedly. The formation of H-bonded bimolecular pre-reaction complexes is the initial stage of the gas-phase reactions; at the same time, no indications of the formation of stable π-complexes were found on the potential energy surfaces of systems under study. The calculated energy barriers to the gasphase reactions exceed 40 kcal mol−1, while those to reactions in the complex XH…H2CO…HC(O)OH (X=OH, F) become more than halved.

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References

  1. W. P. Jencks,Catalysis in Chemistry and Biochemistry, McGraw-Hill, New York, 1969.

    Google Scholar 

  2. A. J. Kirby,Angew. Chem., Int. Ed. Engl., 1996,35, 707;Adv. Phys. Org. Chem. 1994,29, 87.

    Article  CAS  Google Scholar 

  3. V. I. Minkin, B. Ya. Simkin, and R. M. Minyaev,Quantum Chemistry of Organic Compounds. Mechanisms of Reactions, Springer-Verlag, Berlin, 1990, 270 pp.

    Google Scholar 

  4. H. B. Burgi and J. D. Dunitz,Acc. Chem. Res., 1983,16, 153.

    Article  Google Scholar 

  5. Y.-T. Chang and G. H. Loew,J. Am. Chem. Soc., 1994,116, 3548.

    Article  CAS  Google Scholar 

  6. R. M. Minyaev,Izv. Akad. Nauk, Ser. Khim., 1998, 13 [Russ. Chem. Bull., 1998,47, 8 (Engl. Transl.)].

  7. A. Fiedler, D. Schroder, H. Schwarz, B. L. Tjelta, and P. B. Armentrout,J. Am. Chem. Soc., 1996,118, 5047.

    Article  CAS  Google Scholar 

  8. O. N. Ventura, E. L. Coitino, A. Lledos, and J. Bertran,J. Comput. Chem., 1992,13, 1037.

    Article  CAS  Google Scholar 

  9. R. M. Minyaev,Usp. Khim., 1994,63, 939 [Russ. Chem. Rev., 1994,63, 883 (Engl. Transl.)].

    CAS  Google Scholar 

  10. H. Yamataka, S. Nagase, T. Ando, and T. Nanafusa,J. Am. Chem. Soc., 1986,108, 601.

    Article  CAS  Google Scholar 

  11. I. H. Williams,Chem. Soc. Rev., 1993,22, 277.

    Article  CAS  Google Scholar 

  12. C. Kozmutza, E. M. Evleth, and E. Kapuy,J. Mol. Struct. (Theochem.), 1991,233, 139.

    Article  Google Scholar 

  13. F. Leng, R. Savkur, I. Fokt, T. Przewloka, W. Priebe, and J. B. Chaires,J. Am. Chem. Soc., 1996,118, 4731 (and references cited therein).

    Article  CAS  Google Scholar 

  14. F. A. Baiocchi and W. Klemperer,J. Chem. Phys., 1983,78, 3509.

    Article  CAS  Google Scholar 

  15. L. Schriver, O. Abdelaoui, and A. Schriver,J. Chem. Phys., 1992,96, 8069.

    Article  CAS  Google Scholar 

  16. O. Abdelaoui, L. Schriver, and A. Schriver,J. Mol. Struct., 1992,268, 335.

    Article  CAS  Google Scholar 

  17. A. Nowek and J. Leszczynski,J. Chem. Phys., 1996,104, 1441.

    Article  CAS  Google Scholar 

  18. T. Yamabe, C.-D. Zhao, M. Koizumi, A. Tachibana, and K. Fukui,Can. J. Chem., 1985,63, 1532.

    Article  CAS  Google Scholar 

  19. K. Yamashita, T. Yamabe, and K. Fukui,Theor. Chim. Acta, 1982,60, 523.

    Article  CAS  Google Scholar 

  20. J. D. Madura and W. L. Jorgensen,J. Am. Chem. Soc., 1986,108, 2517.

    Article  CAS  Google Scholar 

  21. J. B. Foresman and E. Frisch,Exploring Chemistry with Electronic Structure Methods, 2nd Ed., Gaussian, Inc., Pittsburgh, 1996, 302 pp.

    Google Scholar 

  22. M. J. Frish, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. AlLaham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople,GAUSSIAN-94, Revision B.3, Gaussian, Inc., Pittsburgh (PA), 1995.

    Google Scholar 

  23. 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, and J. A. Montgomery,J. Comput. Chem., 1993,14, 1347.

    Article  CAS  Google Scholar 

  24. K. S. Krasnov, N. V. Filippenko, V. A. Bobkova, N. L. Lebedeva, E. V. Morozov, T. I. Ustinova, and G. A. Romanova,Molekulyarnye postoyannye neorganicheskikh soedinenii [Molecular Constants of Inorganic Compounds], Khimiya, Leningrad, 1979, 446 pp. (in Russian).

    Google Scholar 

  25. Y. Yamada, T. Nakagawa, K. Kuchisu, and Y. Morino,J. Mol. Spectrosc., 1971,38, 70.

    Article  CAS  Google Scholar 

  26. J. L. Derissen,J. Mol. Struct., 1971,7, 67.

    Article  CAS  Google Scholar 

  27. A. D. Buckingham,J. Mol. Struct., 1991,250, 111.

    Article  CAS  Google Scholar 

  28. D. E. Reisner, R. W. Field, J. L. Kinsey, and H.-L. Dai,J. Chem. Phys., 1984,80, 5968.

    Article  CAS  Google Scholar 

  29. O. A. Osipov, V. I. Minkin, and A. D. Garnovskii,Spravochnik po dipol'nym momentam [Handbook of Dipole Moments], Vysshaya Shkola, Moscow, 1971, 414 pp. (in Russian).

    Google Scholar 

  30. T. K. Ha, J. Makarewicz, and A. Bauder,J. Chem. Phys., 1993,97, 11415.

    Article  CAS  Google Scholar 

  31. I. H. Williams,J. Am. Chem. Soc., 1987,109, 6299.

    Article  CAS  Google Scholar 

  32. B. J. Nelander,J. Chem. Phys., 1980,72, 77;Chem. Phys., 1992,159, 281.

    Article  CAS  Google Scholar 

  33. E. E. Astrup,Acta Chem. Scand., 1971,25, 1494.

    Article  CAS  Google Scholar 

  34. A. C. Legon and D. J. Millen, inPrinciples of Molecular Recognition, Eds. A. D. Buckingham, A. C. Legon, and S. M. Roberts, Blackie Academic and Professional, London, 1993, 16.

    Google Scholar 

  35. T. Steiner, J. A. Kanter, and J. Kroon,J. Chem. Soc., Chem. Commun., 1996, 1277.

  36. G. A. Jeffrey and W. Saenger,Hydrogen Bonding in Biological Structures, Springer-Verlag, New York, 1991, 569 pp.

    Google Scholar 

  37. R. M. Lees and J. G. Baker,J. Chem. Phys., 1968,48, 5299.

    Article  CAS  Google Scholar 

  38. D. R. Herschbach,J. Chem. Phys., 1956,25, 358.

    Article  CAS  Google Scholar 

  39. R. M. Minyaev and E. A. Lepin,Mendeleev Commun., 1997, 80, 189 ftp://soul.rnd.runnet.ru/pub/gorguts.zip|url

    Article  Google Scholar 

  40. F. Hibbert,Adv. Phys. Org. Chem., 1986,22, 113.

    Article  CAS  Google Scholar 

  41. M. C. Etter,J. Phys. Chem., 1991,95, 4601.

    Article  CAS  Google Scholar 

  42. S. Scheiner,Acc. Chem. Res., 1994,27, 402.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Institute of Physical and Organic Chemistry, Rostov State University, 194/2 prosp. Stachki, 344090, Rostov-on-Don, Russian Federation

    R. M. Minyaev, A. G. Starikov & E. A. Lepin

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  1. R. M. Minyaev
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  2. A. G. Starikov
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  3. E. A. Lepin
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2146–2154, November, 1998.

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Minyaev, R.M., Starikov, A.G. & Lepin, E.A. Pathways of the reactions of nucleophilic addition of H2O and HF molecules to formaldehyde in the gas phase and in the complex with formic acid:ab initio calculations. Russ Chem Bull 47, 2078–2086 (1998). https://doi.org/10.1007/BF02494259

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