TY - JOUR
T1 - Oxidative addition of carbon-carbon bonds with a redox-active Bis(imino)pyridine iron complex
AU - Darmon, Jonathan M.
AU - Stieber, S. Chantal E.
AU - Sylvester, Kevin T.
AU - Fernández, Ignacio
AU - Lobkovsky, Emil
AU - Semproni, Scott P.
AU - Bill, Eckhard
AU - Wieghardt, Karl
AU - Debeer, Serena
AU - Chirik, Paul J.
PY - 2012/10/17
Y1 - 2012/10/17
N2 - Addition of biphenylene to the bis(imino)pyridine iron dinitrogen complexes, (iPrPDI)Fe(N2)2 and [( MePDI)Fe(N2)]2(μ2-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.
AB - Addition of biphenylene to the bis(imino)pyridine iron dinitrogen complexes, (iPrPDI)Fe(N2)2 and [( MePDI)Fe(N2)]2(μ2-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.
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U2 - 10.1021/ja306526d
DO - 10.1021/ja306526d
M3 - Article
C2 - 23043331
AN - SCOPUS:84867520736
SN - 0002-7863
VL - 134
SP - 17125
EP - 17137
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 41
ER -