Catalyzed autoxidation of hydrogensulfite by cobalt(II) (2,3,9,10-tetramethyl-1,4,8,11-tetraaza-cyclotetradeca-1,3,8,10-tetraene) (H2O)22+

Ela Solomon-Rapaport, Alexandra Masarwa, Haim Cohen, Dan Meyerstein

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The catalytic autoxidation of hydrogensulfite (hydrogen-trioxosulfate(1-)) in the presence of Co(tim)(H2O)22+ (tim = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) was studied. Dioxygen reacts with excess sulfite in the presence of Co(tim)(H2O)22+ in a complex process (a minimum of five kinetic steps can be identified) to produce Co(tim)(SO3)x(3-2x)+ (x = 1 or 2) (λmax at 350 nm) and sulfate. Seventy turnovers over 4 h were attained in a system where dioxygen and sulfite were supplied constantly. The Co(III) product formed reacts only slowly with dioxygen to produce sulfate. A mechanistic analysis of the results implies the involvement of a Co(tim)-dioxygen adduct, stabilized by an axial sulfite ligand.

Original languageEnglish
Pages (from-to)221-229
Number of pages9
JournalSupramolecular Chemistry
Issue number2-3
StatePublished - 2002
Externally publishedYes

Bibliographical note

Funding Information:
This study was supported in part by a grant from the Budgeting and Planning Committee of The Council of Higher Education and the Israel Atomic Energy Commission. D. M. wishes to express his thanks to Mrs Irene Evens for her ongoing interest and support.


  • Catalyzed autoxidation
  • Cobalt complexes
  • Dioxygen
  • Sulfite (hydrogentrioxosulfate(1-))


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