Laurence Grimaud

Metallaphotoredox catalyzed cross‐coupling of an arylbromide (Ar−Br) with an alkyl bis(catecholato)silicate (R−Si ⊖ ) has been analyzed in depth using a continuum of analytical techniques (EPR, fluorine NMR, electrochemistry, photophysics) and modeling (micro‐kinetics and DFT calculations). These studies converged on the impact of four control parameters consisting in the initial concentrations of the iridium photocatalyst ([Ir] 0 ), nickel precatalyst ([Ni] 0 ) and silicate ([R−Si ⊖ ] 0 ) as well as light intensity I 0 for an efficient reaction between Ar−Br and R−Si ⊖ . More precisely, two regimes were found to be possibly at play. The first one relies on an equimolar consumption of Ar−Br with R−Si ⊖ smoothly leading to Ar−R, with no side‐product from R−Si ⊖ and a second one in which R−Si ⊖ is simultaneously coupled to Ar−Br and degraded to R−H. This integrative approach could serve as a case study for the investigation of other metallaphotoredox catalysis manifolds of synthetic significance.