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Issue 8, 2015
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Fe(IV) alkylidenes via protonation of Fe(II) vinyl chelates and a comparative Mössbauer spectroscopic study

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Abstract

Treatment of cis-Me2Fe(PMe3)4 with di-1,2-(E-2-(pyridin-2-yl)vinyl)benzene ((bdvp)H2), a tetradentate ligand precursor, afforded (bdvp)Fe(PMe3)2 (1-PMe3) and 2 equiv. CH4, via C–H bond activation. Similar treatments with tridentate ligand precursors PhCH[double bond, length as m-dash]NCH2(E-CH[double bond, length as m-dash]CHPh) ((pipp)H2) and PhCH[double bond, length as m-dash]N(2-CCMe-Ph) ((pipa)H) under dinitrogen provided trans-(pipp)Fe(PMe3)2N2 (2) and trans-(pipvd)Fe(PMe3)2N2 (3), respectively; the latter via one C–H bond activation, and a subsequent insertion of the alkyne into the remaining Fe–Me bond. All three Fe(II) vinyl species were protonated with H[BArF4] to form the corresponding Fe(IV) alkylidene cations, [(bavp)Fe(PMe3)2][BArF4] (4-PMe3), [(piap)Fe(PMe3)3][BArF4] (5), and [(pipad)Fe(PMe3)3][BArF4] (6). Mössbauer spectroscopic measurements on the formally Fe(II) and Fe(IV) derivatives revealed isomer shifts within 0.1 mm s−1, reflecting the similarity in their bond distances.

Graphical abstract: Fe(iv) alkylidenes via protonation of Fe(ii) vinyl chelates and a comparative Mössbauer spectroscopic study

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Publication details

The article was received on 08 Apr 2015, accepted on 20 May 2015 and first published on 20 May 2015


Article type: Edge Article
DOI: 10.1039/C5SC01268F
Citation: Chem. Sci., 2015,6, 4730-4736
  • Open access: Creative Commons BY-NC license
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    Fe(IV) alkylidenes via protonation of Fe(II) vinyl chelates and a comparative Mössbauer spectroscopic study

    B. M. Lindley, A. Swidan, E. B. Lobkovsky, P. T. Wolczanski, M. Adelhardt, J. Sutter and K. Meyer, Chem. Sci., 2015, 6, 4730
    DOI: 10.1039/C5SC01268F

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