Reversible binding of dinitrogen and dioxygen by a ruthenium “picnic-basket” porphyrin

James P. Collman*, John I. Brauman, Jeffrey P. Fitzgerald, John W. Sparapany, James A. Ibers

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

69 Scopus citations


We recently reported the synthesis and characterization of ruthenium “picnic-basket” porphyrin carbonyl complexes. These synthetic tetraarylporphyrins bear a rigid superstructure that defines a molecular cavity on one face of the porphyrin macrocycle. Photolysis of these carbonyl complexes in a coordinating solvent results in formation of bis-solvent complexes. The bis(pyridine) complex has been structurally characterized. General methods to control axial ligation in these ruthenium picnic-basket porphyrins are presented. A transient pentacoordinate ruthenium picnic-basket porphyrin, which reversibly binds both dinitrogen and dioxygen within the protected cavity, has been prepared. The N2 and 02 complexes have been characterized by UV-visible, 1H NMR, and IR spectroscopies. The diamagnetic dioxygen complex shows ν(16O-16O) at 1103 cm−1 and thus is described as containing coordinated superoxide ion. A correlation between dioxygen binding and the Ru(III/II) potential was observed.

Original languageEnglish (US)
Pages (from-to)3486-3495
Number of pages10
JournalJournal of the American Chemical Society
Issue number11
StatePublished - Jan 1 1988

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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