Skip to main content
SpringerLink
Log in

Electrochemical detection of the oxidation of alcohols byN-hydroxyethylethylenediamminetriacetatoruthenate(IV)

  • Full Papers
  • Published:
Transition Metal Chemistry Aims and scope Submit manuscript

Summary

The oxidation of [RuIII(hedta)(H2O)]=(1) to its RuIV monomeric complex at a glassy carbon electrode is abserved to promote oxidation of alcohols bearing an a-hydrogen (i-PrOH benzyl alcohol,sec-phenethyl alcohol). Tertiary substitution blocks the oxidation (t-BuOH). The oxidation of the alcohols is detected by an enhancement in the current of the RuIV/III waves at potentials above 0.96V, caused by scavenging (reduction) of RuIV by the alcohols. Binuclear complexes which possess RuIV bridged by oxo to either a second RuIV or to RuIII in species of composition [LRuORuL]n−, L=hedta3−, fail to oxidize the alcohols. The terminal oxo moiety attached to RuIV is postulated to facilitate the oxidation of primary and secondary alcohols in a manner analogous to Meyer's [RuO(trpy)(bpy)]2+ catalyst. The dissociation of the (III,IV) binuclear complex into its monomers provides a pathway which increases catalytic activity at the expense of the inactive (III, IV) binuclear complex's concentration.

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

Similar content being viewed by others

References

  1. Abbreviations of ligands: hedta3−=N-hydroxyethylethylenediaminetriacetate; edta4−=ethylenediaminetetraacetate; ttha6−=triethylenetetraaminehexaacetate; bpy=2,2′-bipyridine; tryp=2,2′∶6′,2″-terpyridine.

  2. S. Zhang and R.E. Shepherd,Inorg. Chem.,27, 4712 (1988).

    Article  CAS  Google Scholar 

  3. D.T. Sawyer in A.E. Martell and D.T. Sawyer (Eds.),Oxygen Complexes and Oxygen Activation by Transition Metals, Plenum, New York, 1988, pp. 131–148; (b) J.S. Valentine, N.J. Burstyn and L.D. Margerum,ibid., Oxygen Complexes and Oxygen Activation by Transition Metals, Plenum, New York, 1988, pp. 175–187; (c) D. Dolphin in M. G. Simic K. A. Taylor, J.F. Ward and C. von Sonntag (Eds.),Oxygen Radicals in Biology and Medicine, Plenum, New York, 1988, pp. 491–500.

    Google Scholar 

  4. (a) S. Zhang and R.E. Shepherd, submitted toInorg. Chim. Acta, 1991; (b) S. Zhang,Ph.D., Thesis, University of Pittsburgh, USA, 1991.

  5. (a)J.P. Collman, P.D. Hampton and J.I. Brauman,J. Am. Chem. Soc. 112, 2977 (1990); (b)ibid., J.P. Collman, P.D. Hampton and J.I. Brauman,J. Am. Chem. Soc. 112, 2986 (1990),

    Article  CAS  Google Scholar 

  6. A.J. Castellino and T.C. Bruice,J. Am. Chem. Soc. 110, 158 (1987).

    Article  Google Scholar 

  7. T.G. Traylor, Y. Iamamoto, T. Nakano,J. Am. Chem. Soc. 108, 3529 (1986).

    Article  CAS  Google Scholar 

  8. Y. Watanabe and J.T. Groves,J. Am. Chem. Soc. 108, 7834 (1986) and ref. therein.

    Article  Google Scholar 

  9. (a)J.T. Groves, G.A. McClusky, R.E. White and J.J. Coon,J. Biochem. Biophys. Res. Commun.,81, 154 (1978); (b) J.T. Groves in T.G. Spiro (Ed.),Metal Ion Activation of Dioxygen; Metal Ions in Biology, Wiley, New York, 1980, Chapter 3.

    Article  CAS  Google Scholar 

  10. J.P. Collman, J.I. Brauman and T. Kodadek,J. Am. Chem. Soc. 108, 2588 (1986).

    Article  CAS  Google Scholar 

  11. D.C. Heimbrook, S.A. Carr, M.A. Mentzer, E.C. Long and S.M. Hecht,Inorg. Chem. 26, 3836 (1987).

    Article  Google Scholar 

  12. (a)D.C. Heimbrook, R.L. Mulholland and S.M. Hecht,J. Am. Chem. Soc. 108, 7839 (1986); (b) N. Murugeson and S.M. Hecht,J. Am. Chem. Soc.,107, 493 (1985).

    Article  CAS  Google Scholar 

  13. R.B. Baar and F.C. Anson,J. Electroanal. Chem. Interfacial Electrochem.,187, 265 (1985).

    CAS  Google Scholar 

  14. J. Zhou, W. Xi and J.K. Hurst,Inorg. Chem.,29, 160 (1990).

    Article  CAS  Google Scholar 

  15. (a)M.S. Thompson and T.J. Meyer,J. Am. Chem. Soc. 104, 4106 (1982); (b) L. Roecker and T.J. Meyer,J. Am. Chem. Soc.,109, 746 (1987).

    Article  CAS  Google Scholar 

  16. M.S. Thompson and T.J. Meyer,J. Am. Chem. Soc. 104, 5070 (1982). (b) W.K. Seok, J.C. Dobson and T.J. Meyer,Inorg. Chem.,27, 3 (1988).

    Article  CAS  Google Scholar 

  17. (a)B. A. Moyer, B.K. Sipe and T.J. Meyer,Inorg. Chem.,20, 1475 (1981). (b) B.A. Moyer, M.S. Thompson and T.J. Meyer,J. Am. Chem. Soc.,102, 2310 (1980).

    Article  CAS  Google Scholar 

  18. T.J. Meyer,Electrochem. Soc.,131, 221C (1984).

    Article  CAS  Google Scholar 

  19. C.M. Che and V.W.-W. Yam,J. Am. Chem. Soc. 109, 1262 (1987).

    Article  CAS  Google Scholar 

  20. C.M. Che, K.Y. Wong and T.C.W. Mak,J. Chem. Soc. Chem. Commun., 988 (1985).

  21. K.-Y. Wong, C.-M. Che and F.C. Anson,Inorg. Chem.,26, 737 (1987).

    Article  CAS  Google Scholar 

  22. (a)P.A. Leising and J.J. Takeuchi,Inorg. Chem.,26, 4391 (1987) (b) K.J. Takeuchi, G.J. Samuels, S.W. Geisten, J.A. Gilbert, T. Meyer,Inorg. Chem.,22, 1407 (1983).

    Article  CAS  Google Scholar 

  23. (a)M.E. Marmion and K.J. Takeuchi,J. Am. Chem. Soc. 108, 510 (1986), (b) M.E. Marmion and K.J. Takeuchi,J. Chem. Soc. Chem. Commun., 1396 (1987). (c) S.A. Kubow, M.E. Marmion and K.J. Takeuchi,Inorg. Chem.,27, 2761 (1988).

    Article  CAS  Google Scholar 

  24. J.T. Groves and R. Quinn,J. Am. Chem. Soc. 107, 5795 (1985), (1981). (b) J.T. Groves, W.J. Kruper, Jr., R.C. Haushaulter, W. ButlerInorg. Chem. 23, 3846 (1984).

    Article  Google Scholar 

  25. J.T. Groves, K.-H. Ahn and R. Quinn,J. Am. Chem. Soc. 110, 4217 (1988).

    Article  CAS  Google Scholar 

  26. (a)J.P. Collman, C.E. Barnes, P.H. Brothers, T.J. Collins, T. Ozawa, J.C. Gallucci and J.A. Ibers,J. Am. Chem. Soc. 106, 5151 (1984). (b) J.P. Collman, C.E. Barnes, P.N. Swegston and J.A. Ibers,J. Am. Chem. Soc.,106, 3500 (1984).

    Article  CAS  Google Scholar 

  27. M.M. Taqui Khan, M.R.H. Siddiqui, A. Hussain and M.A. Moiz,Inorg. Chem.,25, 2765 (1986). (b) M. M. Taqui Khan, A. Hussain, and G. Ramachandraiah,Inorg. Chem. 25, 3023 (1986).

    Article  Google Scholar 

  28. M.M. Taqui Khan, R.S. Shukla and A.P. Rao,Inorg. Chem.,28, 452 (1989).

    Article  Google Scholar 

  29. S. Perrier, T.C. Lau and J.K. Kochi,Inorg. Chem.,29, 4190 (1990).

    Article  CAS  Google Scholar 

  30. (a)K.R. Seddon and E.A. Sheddon,The Chemistry of Ruthenium; Monograph 19, Elsevier: Amsterdam, 1984. (b) R.A. Sheldon, J.K. Kochi,Metal Centered Oxidation of Organic Compounds; Academic, New York, 1981.

    Google Scholar 

  31. P.H.J. Carlsen, T. Katsuki, V.S. Martin and K.B. Sharpless,J. Org. Chem.,46, 3936 (1981).

    Article  CAS  Google Scholar 

  32. T.J. Meyer in A.E. Martell and D.T. Sawyer (Eds.),Oxygen Complexes and Oxygen Activation by Transition Metals, Plenum, New York, 1980, pp. 33–47.

    Google Scholar 

  33. (a)H.C. Bajaj and R. van Eldik,Inorg. Chem.,27, 4052 (1988). (b) H.C. Bajaj and R. van Eldik,Inorg. Chem.,28, 1980 (1989).

    Article  CAS  Google Scholar 

  34. R.E. Shepherd, S. Zhang, P. Dowd, C. Choi, B. Wilks and S.-C. Choi,Inorg. Chim. Acta,174, 256 (1990).

    Article  Google Scholar 

  35. S. Zhang, L.A. Holl and R.E. Shepherd,Inorg. Chem.,29, 1012 (1990).

    Article  CAS  Google Scholar 

  36. M.G. Elliott, S. Zhang and R.E. Shepherd,Inorg. Chem.,28, 3036 (1989).

    Article  CAS  Google Scholar 

  37. R.S. Nicholson and I. Shain,Anal. Chem. 36, 706 (1964).

    Article  CAS  Google Scholar 

  38. A.J. Bard and L.K. Faulkner,Electrochemical Methods, Wiley, New York, 1980, pp. 455–460.

    Google Scholar 

  39. T.R. Cundari and R.S. DragoInorg. Chem.,29, 3904 (1990).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Pittsburgh, 15260, Pittsburgh, Pennsylvania, USA

    Songsheng Zhang, Lori A. Holl & Rex E. Shepherd

Authors
  1. Songsheng Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lori A. Holl
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Rex E. Shepherd
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

TMC 2531

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhang, S., Holl, L.A. & Shepherd, R.E. Electrochemical detection of the oxidation of alcohols byN-hydroxyethylethylenediamminetriacetatoruthenate(IV). Transition Met. Chem. 17, 390–396 (1992). https://doi.org/10.1007/BF02910715

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02910715

Keywords

Search

Navigation