AI Article Synopsis
- The study discusses the activation of a specific iron complex, [FeCl(dppe)Cp], by using sodium salts to abstract chloride, enabling it to react with various nitro aromatics to form new cationic iron-nitroso complexes.
- It also highlights the formation of a unique bimetallic iron complex when reacting with certain amines, suggesting a possible mechanism involving bond cleavage and internal activation processes.
- Notably, the reaction with 4-nitrophenol leads to a stable iron phenolate complex, which is distinguished from typical NO activation pathways, demonstrating a new side of iron chemistry under mild conditions.
Article Abstract
Activation of [FeCl(dppe)Cp] () by chloride abstraction with Na[BAr] (X = F, [B(3,5-(CF)-CH)]; X = Cl, [B(3,5-Cl-CH)]) permits reactions with a range of nitro aromatics, RCHNO (R = halogen, Me, OMe, NO or NMe), to give the cationic iron nitroso complexes [Fe{N(O)-CHR}(dppe)Cp][BAr]) ([][BAr]). Similar reactions of and Na[BAr] with [Fe(NCCHNO)(dppe)Cp][BAr] gave bimetallic [{Fe(dppe)Cp}{μ-N≡CCHN(O)}][BAr]. However, reactions of and Na[BAr] with 4-nitrophenol gave the first example of the bench-stable iron half-sandwich phenolate complex [Fe(OCHNO)(dppe)Cp] rather than NO activation. The formation of complexes [] likely proceeds via the unusual blue bimetallic species [{Fe(dppe)Cp}{μ,κ,'-ONAr}]. This compound undergoes N-O bond cleavage, resulting in [] and a Fe═O species, which reacts via an internal C-H activation of the dppe ligand to give [Fe(κ,,'-P(2-O-CH)(Ph)-CH-PPh)Cp]. Complexes [] are stable under ambient conditions, are readily purified by column chromatography and can be isolated in up to 50% yield, considering that 0.5 equiv of is required as the oxygen acceptor.
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| http://dx.doi.org/10.1021/acs.inorgchem.1c00042 | DOI Listing |
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