Oxidized Bridged Carbenoids as Viable Intermediates in a Fe(III) Catalyzed C−H Insertion Reaction

Abstract

Fe catalyzed carbene insertion reactions present an efficient route for direct CÀ H functionalization. The use of Fe(III) in place of the widely used Fe(II) presents several benefits. However, the mechanistic understanding of Fe(III) severely lags behind Fe(II) complexes. One of the major unsolved issues relates to the formation of bridged versus terminal metallocarbenes. Even though the oxidized bridged carbenoid complexes have been isolated and found to be thermodynamically more stable, they are generally considered a dead end for the catalytic cycle. In the current report, the formation and the subsequent reactions of the bridged carbenoid complexes for an Fe(TPP)Cl catalyzed C(sp 2 )À H insertion are investigated. Using DFT calculations, it is observed that both mono and bis oxidized bridged carbenoid complexes can participate in the catalytic cycle. Importantly, for the first time, a mechanistic pathway showing that these bridged species are not a dead end in Fe catalysis is presented. Their existence in other reactions might be more prevalent than what is currently believed. The current study will have important implications in utilizing Fe(III) complexes for other insertion reactions, especially for heme containing enzymes which necessarily need to be carried out under anaerobic/reducing conditions.