Iron complexes of dendrimer-appended carboxylates for activating dioxygen and oxidizing hydrocarbons

Min Zhao, Brett Helms, Elena Slonkina, Simone Friedle, Dongwhan Lee, Jennifer DuBois, Britt Hedman*, Keith O. Hodgson, Jean M.J. Fréchet, Stephen J. Lippard

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

69 Scopus citations


The active sites of metalloenzymes are often deeply buried inside a hydrophobic protein sheath, which protects them from undesirable hydrolysis and polymerization reactions, allowing them to achieve their normal functions. In order to mimic the hydrophobic environment of the active sites in bacterial monooxygenases, diiron(II) compounds of the general formula [Fe 2([G-3]COO)4(4-RPy)2] were prepared, where [G-3]COO- is a third-generation dendrimer-appended terphenyl carboxylate ligand and 4-RPy is a pyridine derivative. The dendrimer environment provides excellent protection for the diiron center, reducing its reactivity toward dioxygen by about 300-fold compared with analogous complexes of terphenyl carboxylate ([G-1]COO-) ligands. An FeIIFeIII intermediate was characterized by electronic, electron paramagnetic resonance, Mössbauer, and X-ray absorption spectroscopic analyses following the oxygenation of [Fe2-([G-3]COO)4(4-PPy)2], where 4-PPy is 4-pyrrolidinopyridine. The results are consistent with the formation of a superoxo species. This diiron compound, in the presence of dioxygen, can oxidize external substrates.

Original languageEnglish (US)
Pages (from-to)4352-4363
Number of pages12
JournalJournal of the American Chemical Society
Issue number13
StatePublished - Apr 2 2008
Externally publishedYes

ASJC Scopus subject areas

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


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