Double-pillared cobalt Pacman complexes: synthesis, structures and oxygen reduction catalysis

Aline M. J. Devoille, Jason B. Love

Research output: Contribution to journalArticlepeer-review

Abstract

The syntheses and structures of binuclear cobalt complexes of a double-pillared cofacial Schiff-base pyrrole macrocycle (L) were determined and their activity as catalysts for the oxygen reduction reaction evaluated. The new binuclear cobalt complex, [Co-2(L)], 1 was formed in good yield using a salt-elimination method and was characterised as adopting a cofacial structure in solution by NMR spectroscopy and as its THF and pyridine solvates in the solid state by X-ray crystallography. Using a variety of spectroscopic techniques, this complex was found to react reversibly with dioxygen to form a new paramagnetic complex. Furthermore, the new aqua-hydroxy double salt [Co-2(mu-H3O2)(py)(2)(L)][BF4] 2 was characterised by X-ray crystallography. In acidified benzonitrile solution, 1 behaves as a catalyst for the selective four-electron reduction of dioxygen to water and showed a large improvement in efficacy compared to its o-phenylene Schiff-base analogues.

Original languageEnglish
Pages (from-to)65-72
Number of pages8
JournalDalton Transactions
Volume41
Issue number1
DOIs
Publication statusPublished - 7 Jan 2012

Keywords

  • PORPHYRIN-CORROLE DYADS
  • ELECTROCATALYTIC 4-ELECTRON REDUCTION
  • DICOBALT COFACIAL PORPHYRIN
  • SCHIFF-BASE CALIXPYRROLES
  • COUPLED ELECTRON-TRANSFER
  • O BOND ACTIVATION
  • FUEL-CELLS
  • BINUCLEATING LIGANDS
  • HANGMAN PORPHYRINS
  • OXIDATION-STATE

Fingerprint

Dive into the research topics of 'Double-pillared cobalt Pacman complexes: synthesis, structures and oxygen reduction catalysis'. Together they form a unique fingerprint.

Cite this