RESUMO
While iron-NHC catalysed cross-couplings have been shown to be effective for a wide variety of reactions (e.g. aryl-aryl, aryl-alkyl, alkyl-alkyl), the nature of the in situ formed and reactive iron species in effective catalytic systems remains largely undefined. In the current study, freeze-trapped Mössbauer spectroscopy, and EPR studies combined with inorganic synthesis and reaction studies are utilised to define the key in situ formed and reactive iron-NHC species in the Kumada alkyl-alkyl cross-coupling of (2-(1,3-dioxan-2-yl)ethyl)magnesium bromide and 1-iodo-3-phenylpropane. The key reactive iron species formed in situ is identified as (IMes)Fe((1,3-dioxan-2-yl)ethyl)2, whereas the S = 1/2 iron species previously identified in this chemistry is found to be only a very minor off-cycle species (<0.5% of all iron). Reaction and kinetic studies demonstrate that (IMes)Fe((1,3-dioxan-2-yl)ethyl)2 is highly reactive towards the electrophile resulting in two turnovers with respect to iron (kobs > 24 min-1) to generate cross-coupled product with overall selectivity analogous to catalysis. The high resistance of this catalytic system to ß-hydride elimination of the alkyl nucleophile is attributed to its chelation to iron through ligation of carbon and one oxygen of the acetal moiety of the nucleophile. In fact, alternative NHC ligands such as SIPr are less effective in catalysis due to their increased steric bulk inhibiting the ability of the alkyl ligands to chelate. Overall, this study identifies a novel alkyl chelation method to achieve effective alkyl-alkyl cross-coupling with iron(ii)-NHCs, provides direct structural insight into NHC effects on catalytic performance and extends the importance of iron(ii) reactive species in iron-catalysed cross-coupling.
RESUMO
Iron-catalyzed cross-couplings with simple ferric salts have been known since the 1970s, pioneered by Kochi for cross-coupling using alkylmagnesium nucleophiles including MeMgBr. While Kochi observed the formation of a S = 1/2 iron species in reactions of simple ferric salts with MeMgBr proposed to be an iron(I) species, the identity of this species has remained undefined for nearly 40 years. Herein, we report the isolation and characterization of [MgCl(THF)5][Fe8Me12], which combined with EPR and MCD studies is shown to be consistent with Kochi's S = 1/2 species. Reaction studies with ß-bromostyrene demonstrate that this species alone displays minimal reactivity but, when combined with additional MeMgBr, leads to rapid and selective formation of cross-coupled product.
