| Autor: |
Darmon JM; Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14850, USA., Stieber SC, Sylvester KT, Fernández I, Lobkovsky E, Semproni SP, Bill E, Wieghardt K, DeBeer S, Chirik PJ |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of the American Chemical Society [J Am Chem Soc] 2012 Oct 17; Vol. 134 (41), pp. 17125-37. Date of Electronic Publication: 2012 Oct 08. |
| DOI: |
10.1021/ja306526d |
| Abstrakt: |
Addition of biphenylene to the bis(imino)pyridine iron dinitrogen complexes, ((iPr)PDI)Fe(N(2))(2) and [((Me)PDI)Fe(N(2))](2)(μ(2)-N(2)) ((R)PDI = 2,6-(2,6-R(2)-C(6)H(3)-N═CMe)(2)C(5)H(3)N; R = Me, (i)Pr), resulted in oxidative addition of a C-C bond at ambient temperature to yield the corresponding iron biphenyl compounds, ((R)PDI)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. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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