Halogenation is an important alkane functionalization strategy, but O 2 is widely considered the most desirable terminal oxidant. Here, the aerobic iodination of alkanes, including methane, was performed using catalytic [ n Bu 4 N]Cl and light irradiation (390 nm). Up to 10 turnovers of CH 3 I were obtained from CH 4 and air, using a stop-flow microtubing system. Mechanistic studies using cyclohexane as the substrate revealed important details about the iodination reaction. Iodine (I 2 ) serves multiple roles in the catalysis: (1) as the alkyl radical trap, (2) as a precursor for the light absorber, and (3) as a mediator of aerobic oxidation. The alkane activation is attributed to Cl • derived from photofragmentation of the electron donor−acceptor complex of I 2 and Cl − . The kinetic profile of cyclohexane iodination showed that aerobic oxidation of I 3 − to produce I 2 in CH 3 CN is turnoverlimiting.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.