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The iron complex [(bTAML)Fe III -OH 2 ] - ( 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 H 2  18 O, more than 90% of the 18 O-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)Fe IV } 2 -μ-oxo] 2- ( 2 ) dimer from the starting complex 1  via PCET. The subsequent disproportionation of 2 upon addition of substrate, leading to the formation of Fe V (O), renders the high selectivity observed in these reactions.

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