Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Catalytic Effect of $MO_4^{2-_4}$ (M=Cr, Mo and W) on Hydrolyses of Carbon and Phosphorus Esters

  • Published : 20000900
Download PDF
⟨ Previous Next ⟩

Abstract

Second-order rate constants have been measured spectrophotometrically for the hydrolysis of p-nitrophenyl ac-etate (PNPA) and p-nitrophenyl diphenylphosphinate (PNPDPP) with MO42- (M = Cr, Mo and W) in phos-phate buffer (pH = 8.00) at 35.0 $^{\circ}C.$ Thes e MO42- species exhibit large catalytic effect in the hydrolysis of PNPA and PNPDPP except WO42- in the reaction with PNPA. The catalytic effect of these MO42- species has been observed to be much more significantin the hydrolysis of PNPDPP than in the hydrolysis of PNPA. Since the smallest CrO42-would be most highly solvated by H2O molecules, CrO42- is expected to exhibit the least catalytic effect, if solvation effect is the most important factor. However, in fact, CrO42- shows the highest cat-alytic effect toward PNPA, indicating that solvation effect is not solely responsible for the catalytic effect. The most basic CrO42- shows the highest catalytic effect, while the least basic WO42- is least reactive toward PNPA, indicating that the basicity of MO4 2- might bean important factor. However, in the hydrolysis of PNPDPP, no correlation is observed between the basicity and catalytic effect, suggesting thatbasicity alone can not be re-sponsible for the catalytic effect shown by the MO42- species. Formation of a chelate is suggested to be respon-sible for the high catalytic effect of MO42- in the hydrolysis reaction of PNPA and PNPDPP. The formation of chelate is considered to be more suitable for the reaction with PNPDPP than with PNPA based on the larger catalytic effect observed in the reaction with PNPDPP than with PNPA.

Keywords

References

  1. Chem. Soc. Rev. v.10 Jencks, W. P.
  2. Phys. Org. Chem. v.9 Jencks, W. P. J.
  3. J. Org. Chem. v.65 Guha, A. K.;Lee, H. W.;Lee, I.
  4. J. Org. Chem. v.64 Koh, H. J.;Han, K. L.;Lee, I.
  5. J. Org. Chem. v.63 Koh, H. J.;Han, K. L.;Lee, H. W.;Lee, I.
  6. Bull. Korean Chem. Soc. v.16 Lee, D.;Kim, C. K.;Lee, B. S.;Lee, I.
  7. Bull. Korean Chem. Soc. v.5 Lee, I.
  8. Acc. Chem. Res. v.22 Williams, A.
  9. Adv. Phys. Org. Chem. v.27 Williams, A.
  10. Chem. Soc. Rev. v.23 Williams, A.
  11. J. Org. Chem. v.61 Castro, E. A.;Pizzaro, M. I.;Santos, J. G.
  12. J. Org. Chem. v.61 Castro, E. A.;Cubillos, M.;Santos, J. G.
  13. J. Org. Chem. v.62 Castro, E. A.;Araneda, C. A.
  14. J. Phys. Org. Chem. v.4 Correia, V. R.;Cuccovia, I. M.;Chaimovich, H.
  15. Chem. Soc. Rev. v.24 Pregel, M. J.;Dunn, E. J.;Nagelkerke, G. R.;Thatcher, G. R. J.;Buncel, E.
  16. J. Am. Chem. Soc. v.115 Pregel, M. J.; Buncel, E.
  17. J. Am. Chem. Soc. v.113 Pregel, M. J.;Dunn, E. J.;Buncel, E.
  18. Tetrahedron Lett. v.33 Um, I. H.;Yong, J. I.;Kwon, D. S.;Ann, B. T.
  19. Bull. Korean Chem. Soc. v.19 Um, I. H.;Hong, Y. J.;Lee, Y. J.
  20. Bull. Korean Chem. Soc. v.18 Um, I. H.;Lee, Y. J.;Nahm, J. H.;Kwon, D. S.
  21. Bull. Korean Chem. Soc. v.17 Um, I. H.;Nahm, J. H.;Lee, Y. J.;Kwon, D. S.
  22. Bull. Korean Chem. Soc. v.15 Um, I. H.;Lee, S. J.;Park, H. S.;Kwon, D. S.
  23. J. Org. Chem. v.54 Suh, J.;Mun, B. S.
  24. Acc. Chem. Res. v.25 Suh, J.
  25. J. Am. Chem. Soc. v.114 Suh, J.;Park, T.H.;Hwang, B. K.
  26. J. Am. Chem. Soc. v.114 Wikjord, B. R.;Byers, L. D.
  27. J. Am. Chem. Soc. v.114 Wikjord, B. R.;Byers, L. D.
  28. J. Inorg. Nucl. Chem. v.5 Allred, A. L.;Rochow, E. G.
  29. Solid State Chemistry West, A. R.
  30. The Chemists Companion Gordon, A. J.;Ford, R. A.
  31. J. Org. Chem. v.65 Um, I. H.;Min, J. S.;Anh, J. A.;Hahn, H. J.
  32. Can. J. Chem. v.77 Um, I. H.;Min, J. S.;Lee, H. W.
  33. Can. J. Chem. v.76 Um, I. H.;Chung, E. K.;Lee, S. M.
  34. J. Am. Chem. Soc. v.111 Buncel, E.;Um, I. H.;Hoz, S.
  35. Tetrahedron v.53 Um, I. H.;Hong, Y. J.;Kwon, D. S.
  36. Tetrahedron Lett. v.38 Um, I. H.;Chung, E. K.;Kwon, D. S.
  37. Bull. Korean Chem. Soc. v.18 Um, I. H.;Kim, M. J.;Min, J. S.
  38. J. Org. Chem. v.65 Um, I. H.; Buncel, E.
  39. J. Am. Chem. Soc. v.117 Tarkk, R. M.; Buncel, E.

Cited by

  1. Hydrolysis of carboxyesters promoted by vanadium(V) oxyanions vol.40, pp.1, 2011, https://doi.org/10.1039/c0dt00744g
  2. A treatise on Organophosphate pesticide pollution: Current strategies and advancements in their environmental degradation and elimination vol.207, pp.None, 2000, https://doi.org/10.1016/j.ecoenv.2020.111483