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


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 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 NCH2(E-CHCHPh) ((pipp)H2) and PhCHN(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.

SUBMITTER: Lindley BM 

PROVIDER: S-EPMC5667503 | biostudies-literature | 2015 Aug

REPOSITORIES: biostudies-literature

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Fe(iv) alkylidenes <i>via</i> protonation of Fe(ii) vinyl chelates and a comparative Mössbauer spectroscopic study.

Lindley Brian M BM   Swidan Ala'aeddeen A   Lobkovsky Emil B EB   Wolczanski Peter T PT   Adelhardt Mario M   Sutter Jörg J   Meyer Karsten K  

Chemical science 20150520 8


Treatment of <i>cis</i>-Me<sub>2</sub>Fe(PMe<sub>3</sub>)<sub>4</sub> with di-1,2-(<i>E</i>-2-(pyridin-2-yl)vinyl)benzene ((bdvp)H<sub>2</sub>), a tetradentate ligand precursor, afforded (bdvp)Fe(PMe<sub>3</sub>)<sub>2</sub> (<b>1</b>-PMe<sub>3</sub>) and 2 equiv. CH<sub>4</sub>, <i>via</i> C-H bond activation. Similar treatments with tridentate ligand precursors PhCH[double bond, length as m-dash]NCH<sub>2</sub>(<i>E</i>-CH[double bond, length as m-dash]CHPh) ((pipp)H<sub>2</sub>) and PhCH[doub  ...[more]

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