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Issue 11, 2017
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Selective photocatalytic hydroxylation and epoxidation reactions by an iron complex using water as the oxygen source

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Abstract

The iron complex [(bTAML)FeIII–OH2] (1) selectively catalyses the photocatalytic hydroxylation and epoxidation reactions of alkanes and alkenes, respectively, using water as the oxygen-atom source. Upon the oxidation of unactivated alkanes, which included several substrates including natural products, hydroxylation was observed mostly at the 3° C–H bonds with 3° : 2° selectivity up to ∼100 : 1. When alkenes were used as the substrates, epoxides were predominantly formed with high yields. In the presence of H218O, more than 90% of the 18O-labelled oxygen atoms were incorporated into the hydroxylated and epoxide product indicating that water was the primary oxygen source. Mechanistic studies indicate the formation of an active [{(bTAML)FeIV}2-μ-oxo]2− (2) dimer from the starting complex 1via PCET. The subsequent disproportionation of 2 upon addition of substrate, leading to the formation of FeV(O), renders the high selectivity observed in these reactions.

Graphical abstract: Selective photocatalytic hydroxylation and epoxidation reactions by an iron complex using water as the oxygen source

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Publication details

The article was received on 22 Jun 2017, accepted on 02 Sep 2017 and first published on 04 Sep 2017


Article type: Edge Article
DOI: 10.1039/C7SC02780J
Citation: Chem. Sci., 2017,8, 7545-7551
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    Selective photocatalytic hydroxylation and epoxidation reactions by an iron complex using water as the oxygen source

    B. Chandra, K. K. Singh and S. S. Gupta, Chem. Sci., 2017, 8, 7545
    DOI: 10.1039/C7SC02780J

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