Seeing the cis-Dihydroxylating Intermediate: A Mononuclear Nonheme Iron-Peroxo Complex in cis-Dihydroxylation Reactions Modeling Rieske Dioxygenases

The nature of reactive intermediates and the mechanism of the cis-dihydroxylation of arenes and olefins by Rieske dioxygenases and synthetic nonheme iron catalysts have been the topic of intense research over the past several decades. In this study, we report that a spectroscopically well characterized mononuclear nonheme iron(III)-peroxo complex reacts with olefins and naphthalene derivatives, yielding iron(III) cycloadducts that are isolated and characterized structurally and spectroscopically. Kinetics and product analysis reveal that the nonheme iron(III)-peroxo complex is a nucleophile that reacts with olefins and naphthalenes to yield cis-diol products. The present study reports the first example of the cis-dihydroxylation of substrates by a nonheme iron(III)-peroxo complex that yields cis-diol products.

Automated summary

The nature of reactive intermediates and the cis-dihydroxylation mechanism of arenes and olefins have been studied extensively in the past few decades. In this study, the reaction between a spectroscopically characterized mononuclear nonheme iron(III)-peroxo complex and olefins and naphthalene derivatives has been investigated. The results show that the nonheme iron(III)-peroxo complex is a nucleophile and reacts with olefins and naphthalenes to yield cis-diol products. This study presents the first example of cis-dihydroxylation of substrates by a nonheme iron(III)-peroxo complex.