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Examination of Cobalt “Picket Fence” Porphyrin and Its Complex with 1-Methylimidazole as Catalysts for the Electroreduction of Dioxygen

Steiger, Beat and Anson, Fred C. (2000) Examination of Cobalt “Picket Fence” Porphyrin and Its Complex with 1-Methylimidazole as Catalysts for the Electroreduction of Dioxygen. Inorganic Chemistry, 39 (20). pp. 4579-4585. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20170425-063336725

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Abstract

The electrochemical behavior of cobalt 5,10,15,20-tetrakis(α,α,α,α-2-pivalamidophenyl)porphyrin (Co^(II)TpivPP) was examined in benzonitrile solutions. The electrochemical responses were changed significantly by the addition of 1-methylimidazole which coordinates once to the Co(II) and twice to the Co(III) porphyrin. The corresponding equilibrium binding constants were estimated as 2.9 × 10^3 M^(-1) and 1.7 × 10^(20) M^(-2). The cyclic voltammetric responses were affected by the rates of the ligand association/dissociation reactions. Formation of the O_2 adduct of the Co(II) porphyrin resulted in only small changes in the cyclic voltammetric pattern. Comparison between Co^(II)TpivPP and cobalt tetraphenylporphyrin (Co^(II)TPP) as catalysts for the electroreduction of O_2 showed the latter to be the superior catalyst both when adsorbed on graphite electrodes and when dissolved in thin layers of acidified benzonitrile where Co^(II)TpivPP exhibited unimpressive catalytic activity compared with Co^(II)TPP, which appeared to catalyze the reduction of O_2 by significantly more than 2 electrons per molecule.


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http://dx.doi.org/10.1021/ic000537dDOIArticle
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Additional Information:© 2000 American Chemical Society. Received 22 May 2000. Published online 7 September 2000. Published in print 1 October 2000. This work was supported by the National Science Foundation through a grant to F.C.A. and by the Laboratory for Molecular Sciences, an NSF supported facility at Caltech. Helpful discussions with Drs. Taek Dong Chung, Chunnian Shi, and Shouzhong Zou and with Prof. Ahmed Zewail are acknowledged with pleasure.
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Issue or Number:20
Record Number:CaltechAUTHORS:20170425-063336725
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170425-063336725
Official Citation:Examination of Cobalt “Picket Fence” Porphyrin and Its Complex with 1-Methylimidazole as Catalysts for the Electroreduction of Dioxygen Beat Steiger and Fred C. Anson Inorganic Chemistry 2000 39 (20), 4579-4585 DOI: 10.1021/ic000537d
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ID Code:76890
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:25 Apr 2017 16:43
Last Modified:03 Oct 2019 17:51

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