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

doi:10.1080/10610270290026121

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

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) (λ_max 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 language	English
Pages (from-to)	221-229
Number of pages	9
Journal	Supramolecular Chemistry
Volume	14
Issue number	2-3
DOIs	https://doi.org/10.1080/10610270290026121
State	Published - 1 Jan 2002

Keywords

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

ASJC Scopus subject areas

General Chemistry

Access to Document

10.1080/10610270290026121

Cite this

@article{66340149c1f34615a0bc186f3deeae74,

title = "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+",

abstract = "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.",

keywords = "Catalyzed autoxidation, Cobalt complexes, Dioxygen, Sulfite (hydrogentrioxosulfate(1-))",

author = "Ela Solomon-Rapaport and Alexandra Masarwa and Haim Cohen and Dan Meyerstein",

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.",

year = "2002",

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doi = "10.1080/10610270290026121",

language = "English",

volume = "14",

pages = "221--229",

journal = "Supramolecular Chemistry",

issn = "1061-0278",

publisher = "Taylor and Francis Ltd.",

number = "2-3",

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T1 - 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+

AU - Solomon-Rapaport, Ela

AU - Masarwa, Alexandra

AU - Cohen, Haim

AU - Meyerstein, Dan

N1 - 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.

PY - 2002/1/1

Y1 - 2002/1/1

N2 - 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.

AB - 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.

KW - Catalyzed autoxidation

KW - Cobalt complexes

KW - Dioxygen

KW - Sulfite (hydrogentrioxosulfate(1-))

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DO - 10.1080/10610270290026121

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