Skip to main content

Oxidative Addition of Carbon-Carbon Bonds with a Redox-Active Bis(imino)pyridine Iron Complex

Author(s): Darmon, Jonathan M; Stieber, S Chantal E; Sylvester, Kevin T; Fernandez, Ignacio; Lobkovsky, Emil; et al

To refer to this page use:
Abstract: Addition of biphenylene to the bis(imino)pyridine iron dinitrogen complexes, ((PDI)-P-iPr)Fe(N-2)(2) and [((PDI)-P-Me)Fe(N-2))(2)(mu(2)-N-2) ((PDI)-P-R = 2,6-(2,6-R-2-C6H3- N=CMe)(2)C5H3N; R = Me, Pr-i), resulted in oxidative addition of a C C bond at ambient temperature to yield the corresponding iron biphenyl compounds, ((PDI)-P-R)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 Mossbauer 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.
Publication Date: 17-Oct-2012
Citation: Darmon, Jonathan M, Stieber, S Chantal E, Sylvester, Kevin T, Fernandez, Ignacio, Lobkovsky, Emil, Semproni, Scott P, Bill, Eckhard, Wieghardt, Karl, DeBeer, Serena, Chirik, Paul J. (2012). Oxidative Addition of Carbon-Carbon Bonds with a Redox-Active Bis(imino)pyridine Iron Complex. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 134 (17125 - 17137. doi:10.1021/ja306526d
DOI: doi:10.1021/ja306526d
ISSN: 0002-7863
Pages: 17125 - 17137
Type of Material: Journal Article
Version: Author's manuscript

Items in OAR@Princeton are protected by copyright, with all rights reserved, unless otherwise indicated.