Proton exchange between oxymethyl radical and acids and bases: semiempirical quantum-chemical study

  • Irina Anatolievna Pustolaikina Karaganda State University named after E.A. Buketov, Karaganda http://orcid.org/0000-0001-6319-666X
  • Kamshat Zhambylovna Kutzhanova Karaganda State University named after E.A. Buketov, Karaganda
  • Irina Leonidovna Stadnik Karaganda State University named after E.A. Buketov, Karaganda
  • Alfia Faridovna Kurmanova Karaganda State University named after E. A. Buketov, Karaganda

Abstract

The reactions with proton participation are widely represented in the analytical, technological and biological chemistry. Quantum-chemical study of the exchange processes in hydrogen bonding complexes will allow us to achieve progress in the understanding of the elementary act mechanism of proton transfer in hydrogen bonding chain as well as the essence of the acid-base interactions. Oxymethyl radical •CH2ОН is small in size and comfortable as a model particle that well transmits protolytic properties of paramagnetic acids having more complex structure. Quantum-chemical modeling of proton exchange reaction oxymethyl radical ∙CH2OH and its diamagnetic analog CH3OH with amines, carboxylic acids and water was carried out using UAM1 method with the help of Gaussian-2009 program. QST2 method was used for the search of transition state, IRC procedure was applied for the calculation of descents along the reaction coordinate. The difference in the structure of transition states of ∙CH2OH/ CH3OH with bases and acids has been shown. It has been confirmed that in the case of bases, consecutive proton exchange mechanism was fixed, and in the case of complexes with carboxylic acids parallel proton exchange mechanism was fixed. The similarity in the reaction behavior of paramagnetic and diamagnetic systems in the proton exchange has been found. It was suggested that the mechanism of proton exchange reaction is determined by the structure of the hydrogen bonding cyclic complex, which is, in turn, depends from the nature of the acid-base interactions partners.

Author Biographies

Irina Anatolievna Pustolaikina, Karaganda State University named after E.A. Buketov, Karaganda
Department of Physical and Analytical Chemistry, Associate Professor
Kamshat Zhambylovna Kutzhanova, Karaganda State University named after E.A. Buketov, Karaganda
Department of Physical and Analytical Chemistry, Associate Professor
Irina Leonidovna Stadnik, Karaganda State University named after E.A. Buketov, Karaganda
Department of Physical and Analytical Chemistry, Senior Lecturer
Alfia Faridovna Kurmanova, Karaganda State University named after E. A. Buketov, Karaganda
Department of Physical and Analytical Chemistry, Associate Professor

References

1      Bell RP (1977) Proton in Chemistry [Proton v himii]. Mir, Moscow, Russia. (In Russian)

2      George C Pimentel, Aubrey L McClellan (1960) The hydrogen bond. W.H.Freeman & Co Ltd, San Francisco and London, UK. ISBN 978-0-71670-113-2

3      Scheiner S (1997) Hydrogen Bonding: A Theoretical Perspective. Oxford University Press, New York, USA. ISBN 978-0-19509-011-6

4      Kaplan IG (2012) Intermolecular interactions. The physical interpretation, computer simulations and modeling capabilities [Mezhmolekuljarnye vzaimodejstvija. Fizicheskaja interpretacija, komp'juternye raschety i model'nye potenciali]. BINOM, Laboratorija znanij, Moscow, Russia. (In Russian). ISBN 978-5-94774-939-7

5      Kessler YM, Petrenko VE, Lyashenko AK, etc. (2003) Water: structure, state, solvation. Recent achievements [Voda: struktura, sostojanie, sol'vatacija. Dostizhenija poslednih let], ed. by Kutepov AM. Nauka, Moscow, Russia. (In Russian). ISBN 5-02-006485-8 

6       (1974) Investigation of rates and mechanisms of reactions, ed. by Hammes GG. Wiley, New York, USA. ISBN 978-0-47193-095-2

7      Weil JA, Bolton JR (2007) Electron paramagnetic resonance: Elementary theory and applications, 2nd Edition. Wiley, John & Sons, New York, USA. ISBN 978-0471754961

8      Kawamuri A, Yamauci J, Ohta H (2002) EPR in the 21 Century. Elsevier Science, Amsterdam, Netherlands. ISBN 978-0-444-50973-4

9      Nikolskiy SN (2010) EPR spectroscopy of protolytic reactions kinetics in solutions of organic acids and bases [EPR-spektroskopija kinetiki protoliticheskih reakcij v rastvorah organicheskih kislot i osnovanij]. Abstract of dissertation for Doctor of Chemical Sciences Degree. Karaganda, Kazakhstan. (In Russian)

10   Masalimov AS, Tur AA, Nikolskiy SN (2016) Theoretical and Experimental Chemistry  52:57-65. (In Russian). http://dx.doi.org/10.1007/s11237-016-9451-0

11  Fischer Н (1965) Mol Phys 9:149-152. http://dx.doi.org/10.1080/00268976500100161

12  Silverstein R, Webster F, Kiml D (2011) Spectrometric identification of organic compounds [Spektrometricheskaja identifikacija organicheskih soedinenij]. BINOM, Laboratorija znanij, Moscow, Russia. (In Russian). ISBN 978-5-94774-392-0.

13  Berger S, Braun S (2004) 200 and more NMR experiments. Wiley-VCH, Weinheim, Germany.  ISBN 978-3-527-31067-8

14  Ernst RR, Bodenhausen G, Wokaun A (1990) Principles of nuclear magnetic resonance in one and two dimensions. Oxford University Press, Oxford, England. ISBN 978-0-198-55647-3

15  Derome AE (1987) Modern NMR techniques for chemistry research. Pergamon Press, Oxford, UK.  ISBN 978-0-080-32513-2

16  Khramtsov VV, Vainer LM (1988) Russian Chemical Reviews 57:824-838. http://dx.doi.org/10.1070/RC1988v057n09ABEH003393

17  Volodarskiy LB, Grigoriev IA, Dikanov SA, Reznikov VA, Shukin VI (1988) Imidazoline nitroxyl radicals [Imidazolinovye nitroksil'nye radikaly]. Nauka, Novosibirsk, Russia. (In Russian). ISBN 5-02-028677-X

18  Buchachenko AL, Wasserman AM (1973) The stable radicals [Stabil'nye radikaly]. Himija, Moscow, Russia. (In Russian).  

19  Masalimov AS, Melbardis LE, Prokof'ev AI (1993) Russ Chem B+ 42:74-77. http://dx.doi.org/10.1007/BF00699978

20  Laroff GP, Fessenden PW (1973) J Phys Chem 77:1283-1288. http://dx.doi.org/10.1021/j100629a021

21  Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR et al (2009) Gaussian 09, Revision C.01. Gaussian. Inc., Wallingford, CT. http://www.gaussian.com/g_tech/g_ur/m_citation.htm

22  David B Cook (2005) Handbook of computational quantum chemistry. Dover Publications, Mineola, New York, USA. ISBN 978-0-486-44307-2

23  Clark T (1990) Computer chemistry [Komp'juternaja himija]. Mir, Moscow, Russia. (In Russian). ISBN 5-03-001325-3

24  Peng C, Schlegel HB (1993) Israel J Chem 33:449-454. http://dx.doi.org/10.1002/ijch.199300051

25  Peng C, Ayala PY, Schlegel HB, Frisch MJ (1996) J Comput Chem 17:49-56. http://dx.doi.org/10.1002/(SICI)1096-987X(19960115)17:1<49::AID-JCC5>3.0.CO;2-0

26  Fukui K (1981) Accounts Chem Res 14:363-368. http://dx.doi.org/10.1021/ar00072a001

27  Hratchian H. P., Schlegel H. B. (2004) J Chem Phys 120:9918-9924. http://dx.doi.org/10.1063/1.1724823

28  Hratchian HP, Schlegel HB (2005) Journal of Chemical Theory and Computation 1:61-69. http://dx.doi.org/10.1021/ct0499783.

29  Dennington R, Keith T, Millam J (2009) GaussView, version 5. Semichem Inc., Shawnee Mission, KS. http://www.gaussian.com/g_tech/gv5ref/gv5citation.htm

Published
2016-12-30
How to Cite
PUSTOLAIKINA, Irina Anatolievna et al. Proton exchange between oxymethyl radical and acids and bases: semiempirical quantum-chemical study. Chemical Bulletin of Kazakh National University, [S.l.], n. 3-4, p. 22-32, dec. 2016. ISSN 2312-7554. Available at: <http://bulletin.chemistry.kz/index.php/kaznu/article/view/800>. Date accessed: 29 may 2017. doi: https://doi.org/10.15328/cb800.
Section
Physical Chemistry and Electrochemistry

Keywords

proton exchange; proton transfer; oxymethyl radical; complexes by hydrogen bonding; sequential and parallel reaction mechanism, quantum-chemical calculations