Skip to main content
SpringerLink
Log in

DFT investigation of the thermodynamics and mechanism of electrophilic chlorination and iodination of arenes

  • Original Paper
  • Published:
Journal of Molecular Modeling Aims and scope Submit manuscript

Abstract

Quantum chemical calculations at the B3LYP/6-311G* level have been carried out in order to investigate the reaction mechanisms of the iodination of benzene and its monosubstituted derivatives with ICl, I+, I +3 and reagents containing N–I and O–I bonds as the iodinating agents. The results are compared with those obtained for chlorination by Cl+ and Cl2, both in the gas phase and in methanol solution using the PCM solvent model. We have also used the MP2/DGDZVP level of theory and the IEFPCM model to perform comparisons in a few cases. The thermodynamic parameters for the reactions have been calculated, the structures of the intermediate products (π- and σ-complexes) and transition states have been optimized, and the profiles of the free energy surfaces have been constructed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Li JJ, Gribble WG (2000) Palladium in heterocyclic chemistry. A guide for the synthetic chemist. Tetrahedron Org Chem Ser 20:1–413

    Google Scholar 

  2. Söderberg BC, Coord G (2004) Transition metals in organic synthesis. Chem Rev 248:1085–1158

    Google Scholar 

  3. Bellina F, Carpita A, Rossi R (2004) Palladium catalysts for the Suzuki cross-coupling reaction: an overview of recent advances. Synthesis 2419–2440

  4. Guiry P, Kiely D (2004) The development of the intramolecular asymmetric Heck reaction. Curr Org Chem 8:781–794

    Google Scholar 

  5. Volkert WA, Hoffman TJ (1999) Therapeutic radiopharmaceuticals. Chem Rev 99:2269–2292

    Google Scholar 

  6. Yu SV, Watson AD (1999) Metal-based X-ray contrast media. Chem Rev 99:2353–2377

    Google Scholar 

  7. Filimonov VD, Krasnokutskaya EA, Kh PO, Lesina Yu A (2006) Electronic structures and reactivities of iodinating agents in the gas phase and in solutions: a density functional study. Russ Chem Bull 55:1328–1336

    Google Scholar 

  8. Filimonov VD, Krasnokutskaya EA, Kh PO, Lesina Yu A (2008) Theoretical analysis of the reactions of electrophilic iodination and chlorination of benzene and polycyclic arenes in the approximation of density functional theory. Russ J Org Chem 33:681–686

    Google Scholar 

  9. Kh PO, Yureva AG, Filimonov VD, Frenking G (2009) Study of a surface of the potential energy for processes of alkanes free-radical iodination by B3LYP/DGDZVP method. J Mol Struct THEOCHEM 912:67–72

    Article  Google Scholar 

  10. Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652

    Article  CAS  Google Scholar 

  11. Lee C, Yang W, Parr RG (1988) Development of the Colle–Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789

    Google Scholar 

  12. Glukhovtsev MN, Pross A, McGrath MP, Radom L (1995) Extension of Gaussian-2 (G2) theory to bromine- and iodine-containing molecules: use of effective core potentials. J Chem Phys 103:1878–1885

    Article  CAS  Google Scholar 

  13. Tomasi J, Perisco M (2005) Quantum mechanical continuum solvation models. Chem Rev 105:2999–3093

    Article  CAS  Google Scholar 

  14. Frisch MJ, Trucks GW, Schlegel HB, Gill PMW, Johnson BJ, Robb MA, Cheeseman JR, Keith T, Petersson GA, Montgomery JA, Raghavachari K, Al-Laham MA, Zakrzewski V, Ortiz JV, Foresman JB, Closlowski J, Stefanov BB, Nanayakkara A, Challacombe M, Peng CY, Ayala PY, Chen W, Wong MB, Andress JL, Replogle ES, Comperts R, Martin RL, Fox DJ, Binkley JS, Defress DJ, Baker J, Stewart JP, Head-Gordon GC, Pople JA (1998) GAUSSIAN 98, revision A. Gaussian Inc., Pittsburgh

  15. Kirkbride FW (1956) The heats of chlorination of some hydrocarbons and their chloro-derivatives. J Appl Chem 6:11–21

    Article  CAS  Google Scholar 

  16. Kovzel EN, Nesterova TN, Rozhnov AM, Kartavzeva TA (1981) Study of equilibrium in in the chlorobenzene-butylchlorobenzenes systems. Thermodyn Org Comp 65–68

  17. Butler AR, Sanderson AP (1971) Mechanism of aromatic iodination by iodine and nitric Acid. J Chem Soc B 2264–2268

  18. Arotsky J, Mishra HC, Symons MCR (1962) Unstable intermediates. Part XV. Interaction between strong acids and various compounds containing iodine. J Chem Soc 2582–2591

  19. Arotsky J, Darby AC, Hamilton JB (1973) Iodination and iodo-compounds. Part IV. The effect of substituents and solvent composition on the rate of aromatic iodination by means of the tri-iodine cation. J Chem Soc Perkin Trans 2:595–599

    Google Scholar 

  20. Mulliken RS, Person WB (1969) Molecular complexes. Wiley, New York, p 498

  21. Sakai H, Maeda Y, Ichiba S, Negita H (1980) Mossbauer effect of 129I in n-sigma and pi-sigma charge-transfer complexes of iodine in the frozen solution. J Chem Phys 72:6192–6198

    Google Scholar 

  22. Drepaul I, Fagundez V, Guiterrez F, Lau EH, Joens JA (1996) Thermochemistry of molecular complexes of iodine monochloride, iodine monobromide, and bromine with benzene and benzene derivatives. J Org Chem 61:3571–3572

    Article  CAS  Google Scholar 

  23. Su JT, Zewail AH (1998) Solvation ultrafast dynamics of reactions. 14. Molecular dynamics and ab initio studies of charge-transfer reactions of iodine in benzene clusters. J Phys Chem A 102:4082–4099

    Article  CAS  Google Scholar 

  24. Tang LT, Wei Y, Wang Y, Hu SW, Liu XO, Chu TW, Wang XY (2004) A density functional study on the formation of charge transfer complexes between alkaloids and iodine monochloride. J Mol Struct THEOCHEM 686:25–30

    Article  CAS  Google Scholar 

  25. Rosokha SV, Kochi JK (2002) The preorganization step in organic reaction mechanisms. Charge-transfer complexes as precursors to electrophilic aromatic substitutions. J Org Chem 67:1727–1737

    Article  CAS  Google Scholar 

  26. Hubig SM, Kochi JK (2000) Structure and dynamics of reactive intermediates in reaction mechanisms. σ- and π-complexes in electrophilic aromatic substitutions. J Org Chem 65:6807–6818

    Article  CAS  Google Scholar 

  27. Chen R, Cheng YH, Liu L, Li XS, Guo QX (2002) π-Type and σ-type cation–π complexes of atomic cations. Res Chem Intermed 28:41–48

    Google Scholar 

  28. Chen J, Xiao H, Gong X (2003) DFT study on nitration mechanism of benzene with nitronium ion. J Phys Chem A 107:11440–11444

    Article  CAS  Google Scholar 

  29. Sokolov AV (2004) New aspects of electrophylic aromatic substitution mechanism: computational model of nitration reaction. Int J Quant Chem 100:1–12

    Google Scholar 

  30. Ben-Daniel R, de Visser DP, Shaik S, Neumann R (2003) Electrophilic aromatic chlorination and haloperoxidation of chloride catalyzed by polyfluorinated alcohols: a new manifestation of template catalysis. J Am Chem Soc 125:12116–12117

    Article  CAS  Google Scholar 

  31. Wei Y, Wang WB, Hu SW, Chu TW, Tang LT, Liu XQ, Wang Y, Wang XY (2005) Theoretical study of the iodination of methoxybenzene by iodine monochloride. J Phys Org Chem 18:625–631

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Tomsk Polytechnic University, 634050, Tomsk, Russia

    Victor D. Filimonov & Elena A. Krasnokutskaya

  2. Tomsk State Pedagogical University, 634061, Tomsk, Russia

    Oleg Kh Poleshchuk

  3. Philipps-Universität Marburg, 35032, Marburg, Germany

    Gernot Frenking

Authors
  1. Victor D. Filimonov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Oleg Kh Poleshchuk
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Elena A. Krasnokutskaya
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Gernot Frenking
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Oleg Kh Poleshchuk.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Filimonov, V.D., Poleshchuk, O.K., Krasnokutskaya, E.A. et al. DFT investigation of the thermodynamics and mechanism of electrophilic chlorination and iodination of arenes. J Mol Model 17, 2759–2771 (2011). https://doi.org/10.1007/s00894-011-0964-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00894-011-0964-0

Keywords

Search

Navigation