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Generation, Spectroscopic, and Chemical Characterization of an Octahedral Iron(V)-Nitrido Species with a Neutral Ligand Platform

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Weyhermüller,  Thomas
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Bill,  Eckhard
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Sabenya, G., Lázaro, L., Gamba, I., Martin-Diaconescu, V., Andris, E., Weyhermüller, T., et al. (2017). Generation, Spectroscopic, and Chemical Characterization of an Octahedral Iron(V)-Nitrido Species with a Neutral Ligand Platform. Journal of the American Chemical Society, 139(27), 9168-9177. doi:10.1021/jacs.7b00429.


Cite as: http://hdl.handle.net/21.11116/0000-0007-7931-A
Abstract
Iron complex [FeIII(N3)(MePy2tacn)](PF6)2 (1), containing a neutral triazacyclononane-based pentadentate ligand, and a terminally bound azide ligand has been prepared and spectroscopically and structurally characterized. Structural details, magnetic susceptibility data, and Mössbauer spectra demonstrate that 1 has a low-spin (S = 1/2) ferric center. X-ray diffraction analysis of 1 reveals remarkably short Fe–N (1.859 Å) and long FeN–N2 (1.246 Å) distances, while the FT-IR spectra show an unusually low N–N stretching frequency (2019 cm–1), suggesting that the FeN–N2 bond is particularly weak. Photolysis of 1 at 470 or 530 nm caused N2 elimination and generation of a nitrido species that on the basis of Mössbauer, magnetic susceptibility, EPR, and X-ray absorption in conjunction with density functional theory computational analyses is formulated as [FeV(N)(MePy2tacn)]2+ (2). Results indicate that 2 is a low-spin (S = 1/2) iron(V) species, which exhibits a short Fe–N distance (1.64 Å), as deduced from extended X-ray absorption fine structure analysis. Compound 2 is only stable at cryogenic (liquid N2) temperatures, and frozen solutions as well as solid samples decompose rapidly upon warming, producing N2. However, the high-valent compound could be generated in the gas phase, and its reactivity against olefins, sulfides, and substrates with weak C–H bonds studied. Compound 2 proved to be a powerful two-electron oxidant that can add the nitrido ligand to olefin and sulfide sites as well as oxidize cyclohexadiene substrates to benzene in a formal H2-transfer process. In summary, compound 2 constitutes the first case of an octahedral FeV(N) species prepared within a neutral ligand framework and adds to the few examples of FeV species that could be spectroscopically and chemically characterized.