Kinetic Studies on the Oxidation of Oxalatoaquamolybdenum(IV) Trimer by Hydrogen Chromate Ion

수소크롬산 이온에 의한 옥살라토아쿠아몰리브덴(IV) 삼합체의 산화반응

  • Chang-Su Kim (Department of Chemistry Education, Taegu University) ;
  • Chang-Yong Kwon (Department of Chemistry Education, Taegu University)
  • 김창수 (大邱大學敎 師範大學 化學敎育科) ;
  • 권창룡 (大邱大學敎 師範大學 化學敎育科)
  • Published : 1986.02.20

Abstract

Oxidation of $[Mo_3O_4(C_2O_4)_3(H_2O)_3]^{2-}$ with HCr$O_4^-$ yields the molybdenum(Ⅳ) complex, $[Mo_2O_5(C_2O_4)_2(H_2O)_2]^{2-}$. Stoichiometry for the reaction of $[Mo_3O_4(C_2O_4)_3(H_2O)_3]^{2-}$ with HCr$O_4^-$ are expressed as $2Mo_3^{IV} + 4Cr^{VI} {\to} 3Mo_2^{VI} + 4Cr^{III}$. Observed rate constants are dependent on hydrogen ion concentration. The kinetic data are consistent with a mechanism in which three successive single-electron steps convert $Cr^{VI}$to $Cr^{III}$ by way of intermediate $Cr^V$ and $Cr^{IV}$. Detailed mechanisms are presented and discussed.

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References

  1. Inorg. Chem. v.8 R.M. Wing;K.P. Callahan
  2. Quart. Rev. v.20 P.C.H. Mitchell
  3. J. Inorg. Nucl. Chem. v.26 P.C.H. Mitchell
  4. Inorg. Chem. v.3 F.A. Cotton;S.M. Morehouse;J.S. Wood
  5. Inorg. Chem. v.16 G.R. Cayley;R.S. Taylor;R.K. Wharton;A.G. Sykes
  6. J. Am. Chem. Soc. v.82 J.Y. Tong;E.L. King
  7. J. Am. Chem. Soc. v.85 J.H. Espenson;E.L. King
  8. Transition Met. Chem. v.9 C.S. Kim;R. K. Murmann;E.O. Schlemper
  9. J. Am. Chem. Soc. v.102 R.K. Murmann;M.E. Shelton
  10. Inorg. Chem. v.20 M.A. Harmer;D.T. Richens;A.B. Soares;A.T. Thornton;A.G. Sykes
  11. Inorg. Chem. v.12 G.F. McKnight;G.P. Haight, JR.
  12. J. Am. Chem. Soc. v.86 J.H. Espenson
  13. Inorg. Chem. v.22 M.T. Paffett;F.C. Anson
  14. Progress in Inorganic Chemistry v.17 J.K. Beattie;G.P. Haight, JR;S.J. Lippard(Ed.)
  15. Inorg. Chem. v.23 C.S. Kim;R.K. Murmann
  16. J. Am. Chem. Soc. v.100 A. Bino;F.A. Cotton;Z. Dori
  17. J. Chem. Soc. (A) P.C.H. Mitchell
  18. J. Am. Chem. Soc. v.92 J.H. Espenson