Effects of redox potential, steric configuration, solvent, and alkali metal cations on the binding of carbon dioxide to cobalt(I) and nickel(I) macrocycles

Michael H. Schmidt, Gordon M. Miskelly, Nathan S Lewis

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Abstract

The binding of CO2 to metal macrocycles has been determined electrochemically by using cyclic voltammetry or differential pulse polarography. The CO2 binding constants, KCO2, for a series of Co(I) tetraazamacrocycle complexes in (CH3)2SO showed a strong correlation with the Co(II/I) redox potential. Although meso and d,1 stereoisomers of [CoI(Me6[14]4,11-diene)]+ had identical redox potentials, KCO2 differed by a factor of 102 for these stereoisomers, suggesting a large steric effect on CO2 binding. Binding of CO2 to Ni(I) tetraazamacrocycles in (CH3)2SO yielded a redox potential dependence similar to that of Co(I) macrocycles. A weak correlation between KCO2 and the solvent dielectric constant was found for d,l-[Co(Me6[14]-4,11-diene)]+. In tetrahydrofuran (THF), d,l-[Co(Me6[14]4,11-diene)]+ was found to bind CO2 more strongly in the presence of 0.1 M Li+ than in the presence of 0.1 M tetrabutylammonium (TBA+). Electrochemically determined KCO2's for Co(salen)- and Co(Me2salen)- in THF indicated a strong dependence on redox potential and electrolyte cation.

Original languageEnglish
Pages (from-to)3420-3426
Number of pages7
JournalJournal of the American Chemical Society
Volume112
Issue number9
Publication statusPublished - Apr 25 1990

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Alkali Metals
Alkali metals
Cobalt
Nickel
Carbon Dioxide
Oxidation-Reduction
Cations
Carbon dioxide
Positive ions
Stereoisomerism
Polarography
Polarographic analysis
Electrolytes
Cyclic voltammetry
Permittivity
Metals
tetrahydrofuran

ASJC Scopus subject areas

  • Chemistry(all)

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Effects of redox potential, steric configuration, solvent, and alkali metal cations on the binding of carbon dioxide to cobalt(I) and nickel(I) macrocycles. / Schmidt, Michael H.; Miskelly, Gordon M.; Lewis, Nathan S.

In: Journal of the American Chemical Society, Vol. 112, No. 9, 25.04.1990, p. 3420-3426.

Research output: Contribution to journalArticle

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AB - The binding of CO2 to metal macrocycles has been determined electrochemically by using cyclic voltammetry or differential pulse polarography. The CO2 binding constants, KCO2, for a series of Co(I) tetraazamacrocycle complexes in (CH3)2SO showed a strong correlation with the Co(II/I) redox potential. Although meso and d,1 stereoisomers of [CoI(Me6[14]4,11-diene)]+ had identical redox potentials, KCO2 differed by a factor of 102 for these stereoisomers, suggesting a large steric effect on CO2 binding. Binding of CO2 to Ni(I) tetraazamacrocycles in (CH3)2SO yielded a redox potential dependence similar to that of Co(I) macrocycles. A weak correlation between KCO2 and the solvent dielectric constant was found for d,l-[Co(Me6[14]-4,11-diene)]+. In tetrahydrofuran (THF), d,l-[Co(Me6[14]4,11-diene)]+ was found to bind CO2 more strongly in the presence of 0.1 M Li+ than in the presence of 0.1 M tetrabutylammonium (TBA+). Electrochemically determined KCO2's for Co(salen)- and Co(Me2salen)- in THF indicated a strong dependence on redox potential and electrolyte cation.

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