Bio-inspired iron-catalyzed olefin oxidation. Additive effects on the cis-diol/epoxide ratio

Rubén Mas-Ballesté, Megumi Fujita, Carla Hemmila, Lawrence Que

Research output: Contribution to journalArticlepeer-review

26 Scopus citations

Abstract

A landscape of mechanistic possibilities for the oxidation of olefins by bio-inspired non-heme iron catalysts has been explored in this work. The complexes studied consist of iron centers coordinated to the tetradentate N4 ligands tpa and bpmen, which provide two cis-labile sites to the iron center. These complexes catalyze conversion of olefin substrates into epoxide and/or cis-diol products. The diol-to-epoxide ratio is very sensitive to the nature of the tetradentate ligand and reaction conditions. With the aim of understanding how these systems can be modulated, the effects of additives such as water, acetone or acetic acid have been explored. These additives significantly alter the catalytic activity of Fe(bpmen) and Fe(tpa) complexes. Accordingly, the initial mechanistic proposals where the HO-FeV{double bond, long}O intermediate appeared as the unique active oxidizing species have been expanded and other key catalytic intermediates such as FeIII(OOH) or FeIV{double bond, long}O are implicated as a consequence of the results reported in this work.

Original languageEnglish (US)
Pages (from-to)49-53
Number of pages5
JournalJournal of Molecular Catalysis A: Chemical
Volume251
Issue number1-2
DOIs
StatePublished - May 17 2006

Bibliographical note

Funding Information:
The present research is supported by a grant from DOE (FFG02-03ER15455). R.M. thanks the Ministerio de Educación y Ciencia of Spain for postdoctoral support.

Keywords

  • Bpmen
  • Epoxidation
  • Non-heme iron
  • Tpa
  • cis-dihydroxylation

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