Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and C Created by potrace 1.16, written by Peter Selinger 2001-2019 C bonds using water as the oxygen source

An efficient electrochemical method for the selective oxidation of C–H bonds of unactivated alkanes (BDE ≤97 kcal mol −1 ) and C C bonds of alkenes using a biomimetic iron complex, [(bTAML)Fe III -OH 2 ] − , as the redox mediator in an undivided electrochemical cell with inexpensive carbon and nickel electrodes is reported. The O-atom of water remains the source of O-incorporation in the product formed after oxidation. The products formed upon oxidation of C–H bonds display very high regioselectivity (75 : 1, 3° : 2° for adamantane) and stereo-retention (RC ∼99% for cyclohexane derivatives). The substrate scope includes natural products such as cedryl acetate and ambroxide. For alkenes, epoxides were obtained as the sole product. Mechanistic studies show the involvement of a high-valent oxoiron( v ) species, [(bTAML)Fe V (O)] − formed via PCET (overall 2H + /2e − ) from [(bTAML)Fe III -OH 2 ] − in CPE at 0.80 V ( vs. Ag/AgNO 3 ). Moreover, electrokinetic studies for the oxidation of C–H bonds indicate a second-order reaction with the C–H abstraction by oxoiron( v ) being the rate-determining step. A biomimetic iron complex-mediated selective and efficient electrochemical oxygenation of unactivated C–H bonds and C C bonds using water as an O-atom source.