Oxidative addition of carbon-carbon bonds with a redox-active Bis(imino)pyridine iron complex

Jonathan M. Darmon, S. Chantal E. Stieber, Kevin T. Sylvester, Ignacio Fernández, Emil Lobkovsky, Scott P. Semproni, Eckhard Bill, Karl Wieghardt, Serena Debeer, Paul J. Chirik

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127 Scopus citations


Addition of biphenylene to the bis(imino)pyridine iron dinitrogen complexes, (iPrPDI)Fe(N2)2 and [( MePDI)Fe(N2)]22-N2) (RPDI = 2,6-(2,6-R2-6H3=CMe) 2C5H3N; R = Me, iPr), resulted in oxidative addition of a C- bond at ambient temperature to yield the corresponding iron biphenyl compounds, (RPDI)Fe(biphenyl). The molecular structures of the resulting bis(imino)pyridine iron metallacycles were established by X-ray diffraction and revealed idealized square pyramidal geometries. The electronic structures of the compounds were studied by Mössbauer spectroscopy, NMR spectroscopy, magnetochemistry, and X-ray absorption and X-ray emission spectroscopies. The experimental data, in combination with broken-symmetry density functional theory calculations, established spin crossover (low to intermediate spin) ferric compounds antiferromagnetically coupled to bis(imino)pyridine radical anions. Thus, the overall oxidation reaction involves cooperative electron loss from both the iron center and the redox-active bis(imino)pyridine ligand.

Original languageEnglish (US)
Pages (from-to)17125-17137
Number of pages13
JournalJournal of the American Chemical Society
Issue number41
StatePublished - Oct 17 2012

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


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