Fe(iv) alkylidenes via protonation of Fe(ii) vinyl chelates and a comparative Mössbauer spectroscopic study†,10.1039/C5SC01268F

批量搜索

批量搜索

热搜：

Lactoyl-CoA 全氟丁基戊烷白叶藤碱全氟己基辛烷新白叶藤碱壳寡糖特色专题-生物多肽

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

Brian M. Lindley,Ala'aeddeen Swidan,Emil B. Lobkovsky,Peter T. Wolczanski,Mario Adelhardt,Jörg Sutter,Karsten Meyer

Chemical Science Pub Date : 05/20/2015 00:00:00 , DOI:10.1039/C5SC01268F

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-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[BAr^F₄] to form the corresponding Fe(IV) alkylidene cations, [(bavp)Fe(PMe₃)₂][BAr^F₄] (4-PMe₃), [(piap)Fe(PMe₃)₃][BAr^F₄] (5), and [(pipad)Fe(PMe₃)₃][BAr^F₄] (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.