Reaction Kinetics, Mechanisms and Catalysis

, Volume 107, Issue 2, pp 253–261 | Cite as

Application of the Marcus theory to the electron transfer reaction between benzylthioacetic acid and tris(1,10-phenanthroline)iron(III) perchlorate

  • Pathakaraimuthu Balakumar
  • Subramaniam Balakumar
  • Perumal Subramaniam


The electron transfer (ET) reaction between benzylthioacetic acid (BTAA) and tris(1,10-phenanthroline)iron(III) perchlorate resulted in the formation of benzylsulfinylacetic acid. The reaction is first order with respect to both BTAA and [Fe(phen)3]3+ and is retarded by hydrogen ion. The ET reaction is studied in 50 % aqueous methanol medium. The Marcus theory is successfully applied to the present redox system and this supports the operation of single electron transfer in the rate controlling step of the reaction.


Electron transfer reaction Benzylthioacetic acid Marcus theory Tris(1,10-phenanthroline)iron(III) perchlorate 

Supplementary material

11144_2012_481_MOESM1_ESM.doc (107 kb)
Supplementary material 1 (DOC 107 kb)


  1. 1.
    Sheddon RA, Kochi JK (1981) Metal catalysed oxidations of organic compounds. Academic Press, New YorkGoogle Scholar
  2. 2.
    Oritz de Montellano PR (ed) (1995) Cytochrome P-450, structure, mechanism and biochemistry. Plenum Press, New YorkGoogle Scholar
  3. 3.
    Jorgensen KA, Schiott B (1990) Chem Rev 90:1483CrossRefGoogle Scholar
  4. 4.
    Drago RS (1992) Coord Chem Rev 117:185CrossRefGoogle Scholar
  5. 5.
    Canali L, Sherrington DC (1999) Chem Soc Rev 28:85CrossRefGoogle Scholar
  6. 6.
    Samsel EG, Srinivasan K, Kochi JK (1985) J Am Chem Soc 107:7606CrossRefGoogle Scholar
  7. 7.
    Leung WH, Che CM (1989) Inorg Chem 28:4619CrossRefGoogle Scholar
  8. 8.
    Bousquet C, Gilheany DG (1995) Tetrahedron Lett 36:7739CrossRefGoogle Scholar
  9. 9.
    Jacobsen EN (1995) In: Abel EW, Stone FGA, Wilkinson G, Hegedus LS (eds) Comprehensive organometallic chemistry-II, vol 12. Pergamon, New York, p 1097Google Scholar
  10. 10.
    Finney NS, Pospisil PJ, Chang S, Palucki M, Konsler RG, Hansen KB, Jacobsen EN (1997) Angew Chem Int Ed Engl 36:1720CrossRefGoogle Scholar
  11. 11.
    Linde C, Arnold M, Norrby P, Akermark B (1997) Angew Chem Int Ed Engl 36:1723CrossRefGoogle Scholar
  12. 12.
    Jacobsen EN (1993) In: Ojima I (ed) Catalytic asymmetric synthesis. VCH Weinheim, New YorkGoogle Scholar
  13. 13.
    Chellamani A, Alhaji NMI, Rajagopal S (1997) J Chem Soc Perkin Trans 2:299Google Scholar
  14. 14.
    Chellamani A, Kulandaipandi P, Rajagopal S (1999) J Org Chem 64:2232CrossRefGoogle Scholar
  15. 15.
    Baciocchi E, Lanzalunga O, Marconi F (1994) Tetrahedron Lett 35:9771CrossRefGoogle Scholar
  16. 16.
    Fakuzumi S, Nakanishi I, Tanak K, Suenobu T, Tabard A, Guilard R, Caemelbecke EV, Kadish KM (1999) J Am Chem Soc 121:785CrossRefGoogle Scholar
  17. 17.
    Meunier B, Sorokin A (1997) Acc Chem Res 30:470CrossRefGoogle Scholar
  18. 18.
    Marcus RA (1965) J Chem Phys 43:679CrossRefGoogle Scholar
  19. 19.
    Sutin N (1983) Inorg Chem 30:441Google Scholar
  20. 20.
    Guarr T, Mclendon G (1985) Coord Chem Rev 68:1CrossRefGoogle Scholar
  21. 21.
    Barbara PF, Meyer TJ, Ratner MA (1996) J Phys Chem 100:13148CrossRefGoogle Scholar
  22. 22.
    Balzani V (2001) Electron transfer in chemistry. Wiley-VCH, WeinheimCrossRefGoogle Scholar
  23. 23.
    Wong CL, Kochi JK (1979) J Am Chem Soc 101:5593CrossRefGoogle Scholar
  24. 24.
    Ford-Smith MH, Sutin N (1961) J Am Chem Soc 83:1830CrossRefGoogle Scholar
  25. 25.
    Beller G, Lente G, Fabian I (2010) Inorg Chem 49:3968CrossRefGoogle Scholar
  26. 26.
    Eyring H (1935) J Chem Phys 3:107CrossRefGoogle Scholar
  27. 27.
    Lente G, Fabian I, Poe AJ (2005) New J Chem 29:759CrossRefGoogle Scholar
  28. 28.
    Eberson L (1987) Electron transfer reactions in organic chemistry. Springer, HeidelbergCrossRefGoogle Scholar
  29. 29.
    Kochi JK (1990) Acta Chem Scan 44:409CrossRefGoogle Scholar
  30. 30.
    Holland HL (1988) Chem Rev 88:473CrossRefGoogle Scholar
  31. 31.
    Damani LA (eds) (1989) Sulphur containing drugs and related organic compounds—chemistry, biochemistry and toxicology. I(B): metabolism of sulphur functional groups. ChichesterGoogle Scholar
  32. 32.
    Sustin N, Gordon BM (1961) J Am Chem Soc 83:70CrossRefGoogle Scholar
  33. 33.
    George P, Irvine DH (1954) J Chem Soc 587Google Scholar
  34. 34.
    Baxendale JH, Bridge NK (1955) J Phys Chem 59:785CrossRefGoogle Scholar
  35. 35.
    Srinivasan C, Chellamani A, Kuthalingam P (1982) J Org Chem 47:428CrossRefGoogle Scholar
  36. 36.
    Bobrowski GK, Hug GL, Pogocki D, Marciniak B, Schoneich C (2007) J Am Chem Soc 129:9236CrossRefGoogle Scholar
  37. 37.
    Uneyama K, Torii S (1971) Tetrahedron Lett 21:329CrossRefGoogle Scholar
  38. 38.
    Ohe T, Mashino T, Hirobe M (1995) Tetrahedron Lett 42:7681CrossRefGoogle Scholar
  39. 39.
    Weber L, Hommel R, Behling J, Hanfe G, Hannig H (1994) J Am Chem Soc 116:2400CrossRefGoogle Scholar
  40. 40.
    Srinivasan C, Chellamani A, Rajagopal S (1985) J Org Chem 50:1201CrossRefGoogle Scholar
  41. 41.
    Srinivasan C, Rajagopal S, Chellamani A (1990) J Chem Soc Perkin Trans 2:1839Google Scholar
  42. 42.
    Baciocchi E, Intini D, Piermattei A, Rol C, Ruzziconi R (1989) Gazz Chim Ital 119:649Google Scholar
  43. 43.
    Acquaye JH, Muller JG, Takeuchi K (1993) J Inorg Chem 32:160CrossRefGoogle Scholar
  44. 44.
    Watanabe Y, Iyanagi T, Oae S (1980) Tetrahedron Lett 21:3685CrossRefGoogle Scholar
  45. 45.
    Padgette SR, Wimalasena K, Herman HH, Sirimanne SR, May SW (1985) Biochemistry 24:5826CrossRefGoogle Scholar
  46. 46.
    Allen Gnanaraj G, Rajagopal S, Srinivasan C (1992) Ind Acad Sci 104:9Google Scholar
  47. 47.
    Allen Gnanaraj G, Rajagopal S, Srinivasan C, Pitchumani K (1993) Tetrahedron 49:4721CrossRefGoogle Scholar
  48. 48.
    Allen Gnanaraj G, Rajagopal S, Srinivasan C (1994) J Tetrahedron 50:9447CrossRefGoogle Scholar
  49. 49.
    Ruff I, Zimonyi M (1973) Electrochem Acta 18:515CrossRefGoogle Scholar
  50. 50.
    Aderinsewo CO, Adegite A (1979) Inorg Chem 12:3597CrossRefGoogle Scholar
  51. 51.
    Gratzel M (1989) Heterogeneous photochemical electron transfer. CRC Press, Boca RatonGoogle Scholar
  52. 52.
    Sarala R, Stanbury DM (1990) Inorg Chem 29:3456CrossRefGoogle Scholar
  53. 53.
    Sarala R, Stanbury DM (1992) Inorg Chem 3:2771CrossRefGoogle Scholar
  54. 54.
    Sarala R, Rubin SB, Stanbury DM (1991) Inorg Chem 30:3999CrossRefGoogle Scholar
  55. 55.
    Brinck T, Carlqvist P, Holm AH, Dassbjerg K (2002) J Phys Chem A 106:8827CrossRefGoogle Scholar
  56. 56.
    Larsen AG, Holm AH, Roberson M, Daasbjerg K (2001) J Am Chem Soc 123:1723CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2012

Authors and Affiliations

  • Pathakaraimuthu Balakumar
    • 1
  • Subramaniam Balakumar
    • 2
  • Perumal Subramaniam
    • 3
  1. 1.Dr. Sivanthi Aditanar College of EngineeringTiruchendurIndia
  2. 2.PSN College of Engineering and TechnologyTirunelveliIndia
  3. 3.Aditanar College of Arts & ScienceTiruchendurIndia

Personalised recommendations