Solvent Effects on the Solvolysis of cis-$[Co(en)_2ClNO_2]^+$ Ion and Its Mechanism

cis-$[Co(en)_2ClNO_2]^+$ 착이온의 가용매 분해반응에 미치는 용매의 영향과 그 반응 메카니즘

  • Jong-Jae Chung (Department of Chemistry, College of Natural Science, Kyungpook National University) ;
  • Young-Ho Park (Department of Chemistry, College of Natural Science, Kyungpook National University)
  • 정종재 (경북대학교 자연과학대학 화학과) ;
  • 박영호 (경북대학교 자연과학대학 화학과)
  • Published : 1986.02.20

Abstract

The investigation of the effect of solvent structure on the first-order solvolysis of cis-$[Co(en)_2ClNO_2]^+$ion has been extended to water + co-solvent mixtures where the co-solvents are glycerol, ethylene glycol, isopropyl alcohol and t-butyl alcohol. Rates of solvolysis have been evaluated by spectrophotometric method at temperature 25∼30$^{\circ}$C. The polarity of solvent has influence on the variation of rate constant. The non-linear plot of the rate constant in log scale versus $\frac{D-1}{2D+1}$ implies that change in solvent structure with composition plays an important role in determining the variation of rate constant. The linearity of the plot of the rate constant in log scale versus the Grundwald-Winstein Y factor confirms that the solvolysis is an Id-type process with considerable extension of the metal chloride bond in the transition state. In the Kivinen equation the slope of the plot of log k versus $log(H_2O)$ suggests that the solvolysis is also an Id-type process. The application of free energy cycle shows that the effect of solvent structure is greater in the transition state than in the initial state.

Keywords

References

  1. Ann. v.248 A Werner
  2. J. Am. Chem. Soc. v.54 G. Akelof
  3. Chemical Kenetics K.J. Laidler
  4. Inorg. Chem. v.3 C.H. Langford
  5. J. Chem. Soc. (A). J. Burgess;M.G. Price
  6. Acta. Chem. Scand. v.19 A. Kivinen
  7. Adv. Chem. Ser. v.54 C.F. Wells
  8. J. Chem. Soc. Faraday I. v.69 C.F. Wells
  9. J. Chem. Soc. v.A J. Burgess
  10. J. Am. Chem. Soc. v.73 S. Winstein;E. Grunwald;H.W. Jones
  11. J. Chem. Soc. Dalton M. Pribanic;M.Birus;D.Parlovic;S.Asperger
  12. J. Chem. Soc. Faraday I. v.73 C.F.Wells
  13. Mechanism of Inorganic Reaction F. Basolo;R.G. Pearson
  14. J. Chem. Soc. Dalton Gwyn Thomas;Leon A.P.Kane-Maguire
  15. J. Chem. Soc. Faraday trans. I. v.79 G. N. Elgy;C.F. Wells
  16. 日本化學雜誌 v.81 黑田甲子郞
  17. Ann. N.Y. And Acad. Sci. v.39 K.J. Laidler;H.Eyring
  18. J. Chem. Soc. Dalton. C.N. Elgy;C.F. Wells
  19. J. Chem. Soc. E.D. Hughes;C.K. Ingold
  20. J. Chem. Soc. Faraday I. v.71 C.F. Wells
  21. J. Org. Chem. v.43 H. Kwart;T.H. Lilly