Oxidation and reduction of bis(imino)pyridine iron dicarbonyl complexes

Aaron M. Tondreau, Carsten Milsmann, Emil Lobkovsky, Paul J. Chirik

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The oxidation and reduction of a redox-active aryl-substituted bis(imino)pyridine iron dicarbonyl has been explored to determine whether electron-transfer events are ligand- or metal-based or a combination of both. A series of bis(imino)pyridine iron dicarbonyl compounds, [(iPrPDI) Fe(CO)2]-, (iPrPDI)Fe(CO)2, and [(iPrPDI)Fe(CO)2]+ [iPrPDI = 2,6-(2,6-iPr2C6H3N=CMe) 2C5H3N], which differ by three oxidation states, were prepared and the electronic structures evaluated using a combination of spectroscopic techniques and, in two cases, [( iPrPDI)Fe(CO)2]+ and [(iPrPDI)Fe(CO) 2], metrical parameters from X-ray diffraction. The data establish that the cationic iron dicarbonyl complex is best described as a low-spin iron(I) compound (SFe = 1/2) with a neutral bis(imino)pyridine chelate. The anionic iron dicarbonyl, [(iPrPDI) Fe(CO)2]-, is also best described as an iron(I) compound but with a two-electron-reduced bis(imino)pyridine. The covalency of the neutral compound, (iPrPDI)Fe(CO)2, suggests that both the oxidative and reductive events are not ligand- or metal-localized but a result of the cooperativity of both entities.

Original languageEnglish (US)
Pages (from-to)9888-9895
Number of pages8
JournalInorganic Chemistry
Issue number20
StatePublished - Oct 17 2011

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry


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