Issue 8, 2015
From the journal:

Chemical Science

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

Brian M. Lindley,a   Ala'aeddeen Swidan,a   Emil B. Lobkovsky,a   Peter T. Wolczanski,*a   Mario Adelhardt,b   Jörg Sutterb  and  Karsten Meyerb  

* Corresponding authors

a Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY, USA
E-mail: ptw2@cornell.edu
Fax: +1 607 255 4137
Tel: +1 607 255 7220

b Department of Chemistry & Pharmacy, Friedrich Alexander University Erlangen-Nürnberg (FAU), Egerlandstr. 1, D-91058 Erlangen, Germany

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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Article information

DOI
https://doi.org/10.1039/C5SC01268F
Article type
Edge Article
Submitted
08 Apr 2015
Accepted
20 May 2015
First published
20 May 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2015,6, 4730-4736

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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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