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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. and Miskelly, Gordon M. and Lewis, Nathan S. (1990) Effects of redox potential, steric configuration, solvent, and alkali metal cations on the binding of carbon dioxide to cobalt(I) and nickel(I) macrocycles. Journal of the American Chemical Society, 112 (9). pp. 3420-3426. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20180430-145301844

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Abstract

The binding of CO_2 to metal macrocycles has been determined electrochemically by using cyclic voltammetry or differential pulse polarography. The CO_2 binding constants, K for a series of Co(I) tetraammacrocycle complexes in (CH3)_2SO showed a strong correlation with the Co(II/I) redox potential. Although meso and d,l stereoisomers of [Co^I(Me_6[14]4,11- diene)]^+ had identical redox potentials, K_(CO_)2 differed by a factor of 10^2 for these stereoisomers, suggesting a large steric effect on CO_2 binding. Binding of CO_2 to Ni(I) tetraazamacrocycles in (CH_3)_2SO yielded a redox potential dependence similar to that of Co(I) macrocycles. A weak correlation between K_(CO_2) and the solvent dielectric constant was found for d,l-[Co(Me_6[ 14]-4,11 -diene)]^+. In tetrahydrofuran (THF), d,l-[CO(Me_6[14]4,11-diene)]^+ was found to bind CO_2 more strongly in the presence of 0.1 M Li^+ than in the presence of 0.1 M tetrabutylammonium (TBA^+). Electrochemically determined K_(CO_2)'s for Co(salen)^- and Co(Me_2salen)^- in THF indicated a strong dependence on redox potential and electrolyte cation.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/ja00165a027DOIArticle
ORCID:
AuthorORCID
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 1990 American Chemical Society. Received September 14, 1989. We gratefully acknowledge J. Endicott for forwarding a preprint of ref 29 and thank E. Fujita and C. Creutz of Brookhaven National Laboratories for numerous helpful discussions concerning unpublished research on similar systems. We thank B. Balazs for a sample of Ni(cyclam)(ClO_4)_2. This research was funded by the Gas Research Institute. N.S.L. also acknowledges support as a Dreyfus Teacher-Scholar and from the NSF Presidential Young Investigator Program.
Funders:
Funding AgencyGrant Number
Gas Research InstituteUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
NSFUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Division of Chemistry and Chemical Engineering7916
Issue or Number:9
Record Number:CaltechAUTHORS:20180430-145301844
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180430-145301844
Official Citation: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, and Nathan S. Lewis Journal of the American Chemical Society 1990 112 (9), 3420-3426 DOI: 10.1021/ja00165a027
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86137
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:01 May 2018 14:58
Last Modified:03 Oct 2019 19:40

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