A Green‐LED Driven Source of Hydrated Electrons Characterized from Microseconds to Hours and Applied to Cross‐Couplings

We present a novel photoredox catalytic system that delivers synthetically usable concentrations of hydrated electrons when illuminated with a green light‐emitting diode (LED). The catalyst is a ruthenium complex protected by an anionic micelle, and the urate dianion serves as a sacrificial donor confined to the aqueous bulk. By virtue of its chemical properties, this donor not only suppresses charge recombination that would limit the electron yield, but also enables this system to perform cross‐couplings through the action of hydrated electrons, the first examples of which are reported here. We have investigated the kinetics of all the steps involving the electron and its direct precursor in a comparative study by means of laser flash photolysis and by monitoring product formation during LED photolysis. Despite the differences in timescales, each approach on its own already gives a complete picture of the reaction over a temporal range spanning ten orders of magnitude. Discrepancies between the kinetic parameters obtained with the two complementary techniques can be rationalized with the slow secondary chemistry of the system; they reveal that the product‐based method provides a more accurate description because it also responds to the changes of the system composition during a synthesis; hence, they demonstrate that in complex systems the timescale of the experimental observation should be matched to that of the actual application.