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A Self-Assembled Cofacial Cobalt Porphyrin Prism for Oxygen Reduction Catalysis

Oldacre, Amanda N ; Friedman, Alan E ; Cook, Timothy R

Journal of the American Chemical Society, 01 February 2017, Vol.139(4), pp.1424-1427 [Peer Reviewed Journal]

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  • Title:
    A Self-Assembled Cofacial Cobalt Porphyrin Prism for Oxygen Reduction Catalysis
  • Author: Oldacre, Amanda N ; Friedman, Alan E ; Cook, Timothy R
  • Subjects: Cobalt -- Chemistry ; Coordination Complexes -- Chemistry ; Oxygen -- Chemistry ; Porphyrins -- Chemistry
  • Is Part Of: Journal of the American Chemical Society, 01 February 2017, Vol.139(4), pp.1424-1427
  • Description: Herein we report the first study of the oxygen reduction reaction (ORR) catalyzed by a cofacial porphyrin scaffold accessed in high yield (overall 53%) using coordination-driven self-assembly with no chromatographic purification steps. The ORR activity was investigated using chemical and electrochemical techniques on monomeric cobalt(II) tetra(meso-4-pyridyl)porphyrinate (CoTPyP) and its cofacial analogue [Ru(η-iPrCHMe)(dhbq)(CoTPyP)][OTf] (Co Prism) (dhbq = 2,5-dihydroxy-1,4-benzoquinato, OTf = triflate) as homogeneous oxygen reduction catalysts. Co Prism is obtained in one self-assembly step that organizes six total building blocks, two CoTPyP units and four arene-Ru clips, into a cofacial motif previously demonstrated with free-base, Zn(II), and Ni(II) porphyrins. Turnover frequencies (TOFs) from chemical reduction (66 vs 6 h) and rate constants of overall homogeneous catalysis (k) determined from rotating ring-disk experiments (1.1 vs 0.05 h) establish a cofacial enhancement upon comparison...
  • Language: English
  • Identifier: E-ISSN: 1520-5126 ; PMID: 28102678 Version:1 ; DOI: 10.1021/jacs.6b12404
  • Source: MEDLINE/PubMed (U.S. National Library of Medicine)

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